Why does the Conductivity of a Nickel Catalyst Increase during Sulfidation? An Exemplary Study Using an In Operando Sensor Device.

Science.gov (United States)

Fremerey, Peter; Jess, Andreas; Moos, Ralf

2015-10-23

In order to study the sulfidation of a catalyst fixed bed, an in operando single pellet sensor was designed. A catalyst pellet from the fixed bed was electrically contacted and its electrical response was correlated with the catalyst behavior. For the sulfidation tests, a nickel catalyst was used and was sulfidized with H₂S. This catalyst had a very low conductivity in the reduced state. During sulfidation, the conductivity of the catalyst increased by decades. A reaction from nickel to nickel sulfide occurred. This conductivity increase by decades during sulfidation had not been expected since both nickel and nickel sulfides behave metallic. Only by assuming a percolation phenomenon that originates from a volume increase of the nickel contacts when reacting to nickel sulfides, this effect can be explained. This assumption was supported by sulfidation tests with differently nickel loaded catalysts and it was quantitatively estimated by a general effective media theory. The single pellet sensor device for in operando investigation of sulfidation can be considered as a valuable tool to get further insights into catalysts under reaction conditions.

Why does the Conductivity of a Nickel Catalyst Increase during Sulfidation? An Exemplary Study Using an In Operando Sensor Device

Directory of Open Access Journals (Sweden)

Peter Fremerey

2015-10-01

Full Text Available In order to study the sulfidation of a catalyst fixed bed, an in operando single pellet sensor was designed. A catalyst pellet from the fixed bed was electrically contacted and its electrical response was correlated with the catalyst behavior. For the sulfidation tests, a nickel catalyst was used and was sulfidized with H2S. This catalyst had a very low conductivity in the reduced state. During sulfidation, the conductivity of the catalyst increased by decades. A reaction from nickel to nickel sulfide occurred. This conductivity increase by decades during sulfidation had not been expected since both nickel and nickel sulfides behave metallic. Only by assuming a percolation phenomenon that originates from a volume increase of the nickel contacts when reacting to nickel sulfides, this effect can be explained. This assumption was supported by sulfidation tests with differently nickel loaded catalysts and it was quantitatively estimated by a general effective media theory. The single pellet sensor device for in operando investigation of sulfidation can be considered as a valuable tool to get further insights into catalysts under reaction conditions.

Ni Catalysts Supported on Modified Alumina for Diesel Steam Reforming

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Antonios Tribalis

2016-01-01

Full Text Available Nickel catalysts are the most popular for steam reforming, however, they have a number of drawbacks, such as high propensity toward coke formation and intolerance to sulfur. In an effort to improve their behavior, a series of Ni-catalysts supported on pure and La-, Ba-, (La+Ba- and Ce-doped γ-alumina has been prepared. The doped supports and the catalysts have been extensively characterized. The catalysts performance was evaluated for steam reforming of n-hexadecane pure or doped with dibenzothiophene as surrogate for sulphur-free or commercial diesel, respectively. The undoped catalyst lost its activity after 1.5 h on stream. Doping of the support with La improved the initial catalyst activity. However, this catalyst was completely deactivated after 2 h on stream. Doping with Ba or La+Ba improved the stability of the catalysts. This improvement is attributed to the increase of the dispersion of the nickel phase, the decrease of the support acidity and the increase of Ni-phase reducibility. The best catalyst of the series doped with La+Ba proved to be sulphur tolerant and stable for more than 160 h on stream. Doping of the support with Ce also improved the catalytic performance of the corresponding catalyst, but more work is needed to explain this behavior.

Effect study of the support in nickel and cobalt catalysts for obtaining hydrogen from ethanol steam reforming

International Nuclear Information System (INIS)

Silva, Sirlane Gomes da

2013-01-01

A range of oxide-supported metal catalysts have been investigated for the steam reforming of ethanol for the production of hydrogen and subsequent application in fuel cells. The catalysts were synthesized by the co-precipitation and internal gelification methods using cobalt and nickel as active metals supported on aluminum, zirconium, lanthanum and cerium oxides. After prepared and calcined at 550 Cº the solids were fully characterized by different techniques such as X-rays diffraction(DRX), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy, nitrogen adsorption (B.E.T), temperature-programmed reduction in H2 (TPR-H2) and thermogravimetric analysis. The catalytic tests were performed in a monolithic quartz reactor and submitted to different thermodynamic conditions of steam reforming of ethanol at temperatures varying from 500º C to 800 ºC. The product gas streams from the reactor were analyzed by an on-line gas chromatograph. The cobalt/nickel catalyst supported on a ceria-lanthania mixture (Co 10% / Ni 5% - CeO 2 La 2 O 3 ) showed good catalytic performance in hydrogen selectivity reaching a concentration greater than 65%, when compared to other catalytic systems such as: Co 10% / Ni5% - CeO 2 ; Co 10% / Ni 5% - CeO 2 ZrO 2 ; Co 10% / Ni 5% - ZrO 2 ; Co 10% / Ni 5% - La 2 O 3 ; Co 10% / Ni 5% - CeO 2 La 2 O 3 /K 2% ; Co 10 % / Ni 5% - CeO 2 La 2 O 3 / Na 2% ; Ni 10% / Co 5% - CeO 2 La 2 O 3 ; Co-Al 2 O 3 e Co-Al 2 O 3 CeO 2 . (author)

Hydrogen production by dry reforming of methane with carbon dioxide in one-dimensional nickel-based catalysts

International Nuclear Information System (INIS)

Lopez U, A. C.

2016-01-01

The main objective of this thesis is development of nickel catalysts supported over 1D matrix of cerium oxide, to be used in dry reforming methane reaction with carbon dioxide for hydrogen production. The catalysts were characterized by: Temperature Programmed Reduction (TPR), Scanning Electronic Microscopy (Sem), Surface Area (Bet method) an X Ray Diffraction (XRD). The TPR technique allowed to define reduction temperature of the active phase in the catalyst, Sem technique showed that the CeO_2 matrix had a nano rod morphology. XRD allowed to identify the crystalline phases of the catalysts. Finally, the catalysts were tested in the dry reforming methane reaction, high catalytic activity and hydrogen production were performed at 700 degrees Celsius and the catalyst with 30 wt.% of nickel. (Author)

The application of inelastic neutron scattering to investigate the steam reforming of methane over an alumina-supported nickel catalyst

International Nuclear Information System (INIS)

McFarlane, Andrew R.; Silverwood, Ian P.; Norris, Elizabeth L.; Ormerod, R. Mark; Frost, Christopher D.; Parker, Stewart F.; Lennon, David

2013-01-01

Highlights: • Inelastic neutron scattering has been used to investigate a Ni/alumina catalyst. • The extent of hydrogen retention by the catalyst has been determined. • Filamentous carbon is identified as a by-product. - Abstract: An alumina-supported nickel catalyst, previously used in methane reforming experiments employing CO 2 as the oxidant, is applied here in the steam reforming variant of the process. Micro-reactor experiments are used to discern an operational window compatible with sample cells designed for inelastic neutron scattering (INS) experiments. INS spectra are recorded after 6 h reaction of a 1:1 mixture of CH 4 and H 2 O at 898 K. Weak INS spectra are observed, indicating minimal hydrogen retention by the catalyst in this operational regime. Post-reaction, the catalyst is further characterised by powder X-ray diffraction, transmission electron microscopy and Raman scattering. In a comparable fashion to that seen for the ‘dry’ reforming experiments, the catalyst retains substantial quantities of carbon in the form of filamentous coke. The role for hydrogen incorporation by the catalyst is briefly considered

The application of inelastic neutron scattering to investigate the steam reforming of methane over an alumina-supported nickel catalyst

Energy Technology Data Exchange (ETDEWEB)

McFarlane, Andrew R.; Silverwood, Ian P. [School of Chemistry, Joseph Black Building, University of Glasgow, Glasgow G12 8QQ (United Kingdom); Norris, Elizabeth L.; Ormerod, R. Mark [Department of Chemistry, School of Physical and Geographical Sciences, Keele University, Staffs ST5 5BG (United Kingdom); Frost, Christopher D.; Parker, Stewart F. [ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX (United Kingdom); Lennon, David, E-mail: David.Lennon@glasgow.ac.uk [School of Chemistry, Joseph Black Building, University of Glasgow, Glasgow G12 8QQ (United Kingdom)

2013-12-12

Highlights: • Inelastic neutron scattering has been used to investigate a Ni/alumina catalyst. • The extent of hydrogen retention by the catalyst has been determined. • Filamentous carbon is identified as a by-product. - Abstract: An alumina-supported nickel catalyst, previously used in methane reforming experiments employing CO{sub 2} as the oxidant, is applied here in the steam reforming variant of the process. Micro-reactor experiments are used to discern an operational window compatible with sample cells designed for inelastic neutron scattering (INS) experiments. INS spectra are recorded after 6 h reaction of a 1:1 mixture of CH{sub 4} and H{sub 2}O at 898 K. Weak INS spectra are observed, indicating minimal hydrogen retention by the catalyst in this operational regime. Post-reaction, the catalyst is further characterised by powder X-ray diffraction, transmission electron microscopy and Raman scattering. In a comparable fashion to that seen for the ‘dry’ reforming experiments, the catalyst retains substantial quantities of carbon in the form of filamentous coke. The role for hydrogen incorporation by the catalyst is briefly considered.

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.

Intermetallic nickel silicide nanocatalyst-A non-noble metal-based general hydrogenation catalyst.

Science.gov (United States)

Ryabchuk, Pavel; Agostini, Giovanni; Pohl, Marga-Martina; Lund, Henrik; Agapova, Anastasiya; Junge, Henrik; Junge, Kathrin; Beller, Matthias

2018-06-01

Hydrogenation reactions are essential processes in the chemical industry, giving access to a variety of valuable compounds including fine chemicals, agrochemicals, and pharmachemicals. On an industrial scale, hydrogenations are typically performed with precious metal catalysts or with base metal catalysts, such as Raney nickel, which requires special handling due to its pyrophoric nature. We report a stable and highly active intermetallic nickel silicide catalyst that can be used for hydrogenations of a wide range of unsaturated compounds. The catalyst is prepared via a straightforward procedure using SiO 2 as the silicon atom source. The process involves thermal reduction of Si-O bonds in the presence of Ni nanoparticles at temperatures below 1000°C. The presence of silicon as a secondary component in the nickel metal lattice plays the key role in its properties and is of crucial importance for improved catalytic activity. This novel catalyst allows for efficient reduction of nitroarenes, carbonyls, nitriles, N-containing heterocycles, and unsaturated carbon-carbon bonds. Moreover, the reported catalyst can be used for oxidation reactions in the presence of molecular oxygen and is capable of promoting acceptorless dehydrogenation of unsaturated N-containing heterocycles, opening avenues for H 2 storage in organic compounds. The generality of the nickel silicide catalyst is demonstrated in the hydrogenation of over a hundred of structurally diverse unsaturated compounds. The wide application scope and high catalytic activity of this novel catalyst make it a nice alternative to known general hydrogenation catalysts, such as Raney nickel and noble metal-based catalysts.

Hydrogen-water deuterium exchange over metal oxide promoted nickel catalysts

Energy Technology Data Exchange (ETDEWEB)

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

1975-11-01

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

Pulsed laser dewetting of nickel catalyst for carbon nanofiber growth

International Nuclear Information System (INIS)

Guan, Y F; Pearce, R C; Simpson, M L; Rack, P D; Melechko, A V; Hensley, D K

2008-01-01

We present a pulsed laser dewetting technique that produces single nickel catalyst particles from lithographically patterned disks for subsequent carbon nanofiber growth through plasma enhanced chemical vapor deposition. Unlike the case for standard heat treated Ni catalyst disks, for which multiple nickel particles and consequently multiple carbon nanofibers (CNFs) are observed, single vertically aligned CNFs could be obtained from the laser dewetted catalyst. Different laser dewetting parameters were tested in this study, such as the laser energy density and the laser processing time measured by the total number of laser pulses. Various nickel disk radii and thicknesses were attempted and the resultant number of carbon nanofibers was found to be a function of the initial disk dimension and the number of laser pulses

Investigation of the supported nickel catalysts by XAS and XRD, using synchrotron radiation

International Nuclear Information System (INIS)

Aldea, N.; Marginean, P.; Gluhoi, A.; Yaning, Xie; Dong, Bazohong

2001-01-01

In the first part of the paper we present a study based on EXAFS spectroscopy. This method can yield structural information about the local environment around a specific atomic constituent in the amorphous materials, the location and chemical state of any catalytic atom on any support or point defect structures in alloys and composites. EXAFS is a specific technique of the scattering of X-ray on materials. The present study is aimed toward elucidating the local structure of Ni atoms and their interaction with oxide support. In this case, we analyse the first three shells of coordination. The second aim of the paper consists in X-ray diffraction on the same samples. X-ray diffraction method which is capable to determine average particle size, microstrains, probability of faults as well as particle size distribution function of supported Ni catalysts is presented. The method is based on the Fourier analysis of X-Ray diffraction profiles such as (111) (200) and (220). We are going to work out a chemisorption model by the correlation of the local and global structure connected with the specific surface. On the other hand, we will try to estimate specific surface values determined by classical method with occupation factor evaluated by the geometrical Ni clusters. The results obtained on supported nickel catalysts which are used in H/D isotopic exchange reactions are reported. The global structure is obtained with a new fitting method based on the Generalised Fermi Function facilities for approximation and Fourier transform of the experimental X-Ray line profiles. Both types of measurements were performed on Beijing Synchrotron Radiation Facilities (BSRF). (authors)

In situ X-ray absorption fine structure studies on the structure of nickel phosphide catalyst supported on K-USY

CERN Document Server

Kawai, T; Suzuki, S

2003-01-01

Local structure around Ni in a nickel phosphide catalyst supported on K-USY was investigated by an situ X-ray absorption fine structure (XAFS) method during the reduction process of the catalyst and the hydrodesulfurization (HDS) reaction of thiophene. In the passivated sample, Ni phosphide was partially oxidized but after the reduction, 1.1 nm diameter Ni sub 2 P particles were formed with Ni-P and Ni-Ni distances at 0.218 and 0.261 nm, respectively, corresponding to those of bulk Ni sub 2 P. In situ XAFS cleary revealed that the Ni sub 2 P structure was stable under reaction conditions and was an active structure for the HDS process.

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

International Nuclear Information System (INIS)

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

2017-01-01

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

Stable hydrogen production from ethanol through steam reforming reaction over nickel-containing smectite-derived catalyst.

Science.gov (United States)

Yoshida, Hiroshi; Yamaoka, Ryohei; Arai, Masahiko

2014-12-25

Hydrogen production through steam reforming of ethanol was investigated with conventional supported nickel catalysts and a Ni-containing smectite-derived catalyst. The former is initially active, but significant catalyst deactivation occurs during the reaction due to carbon deposition. Side reactions of the decomposition of CO and CH4 are the main reason for the catalyst deactivation, and these reactions can relatively be suppressed by the use of the Ni-containing smectite. The Ni-containing smectite-derived catalyst contains, after H2 reduction, stable and active Ni nanocrystallites, and as a result, it shows a stable and high catalytic performance for the steam reforming of ethanol, producing H2.

Coprecipitated nickel-alumina methanation catalysts

International Nuclear Information System (INIS)

Kruissink, E.C.

1981-01-01

In the last few years there has been a renewed interest in the methanation reaction CO+3H 2 =CH 4 +H 2 O. The investigations described in this thesis were performed in relation to the application of this reaction, within the framework of the so-called 'NFE' project, also called 'ADAM' and 'EVA' project. This project, which has been under investigation in West Germany for some years, aims at the investigation of the feasibility of transporting heat from a nuclear high temperature reactor by means of a chemical cycle. A promising possibility to realize such a cycle exists in applying the combination of the endothermic steam reforming of methane and the exothermic methanation reaction. This thesis describes the investigations into a certain type of methanation catalyst, viz. a coprecipitated nickel-alumina catalyst, with the aim to give more insight into the interrelationship between the preparation conditions on the one hand and catalyst properties such as activity and stability on the other hand. (Auth.)

Study of Supported Nickel Catalysts Prepared by Aqueous Hydrazine Method. Hydrogenating Properties and Hydrogen Storage: Support Effect. Silver Additive Effect; Catalyseurs de nickel supportes prepares par la methode de l'hydrazine aqueuse. Proprietes hydrogenantes et stockage d'hydrogene. Effet du support. Effet de l'ajout d'argent

Energy Technology Data Exchange (ETDEWEB)

Wojcieszak, R

2006-06-15

We have studied Ni or NiAg nano-particles obtained by the reduction of nickel salts (acetate or nitrate) by hydrazine and deposited by simple or EDTA-double impregnation on various supports ({gamma}-Al{sub 2}O{sub 3}, amorphous or crystallized SiO{sub 2}, Nb{sub 2}O{sub 5}, CeO{sub 2} and carbon). Prepared catalysts were characterized by different methods (XRD, XPS, low temperature adsorption and desorption of N{sub 2}, FTIR and FTIR-Pyridine, TEM, STEM, EDS, H{sub 2}-TPR, H{sub 2}-adsorption, H{sub 2}-TPD, isopropanol decomposition) and tested in the gas phase hydrogenation of benzene or as carbon materials in the hydrogen storage at room temperature and high pressure. The catalysts prepared exhibited better dispersion and activity than classical catalysts. TOF's of NiAg/SiO{sub 2} or Ni/carbon catalysts were similar to Pt catalysts in benzene hydrogenation. Differences in support acidity or preparation method and presence of Ag as metal additive play a crucial role in the chemical reduction of Ni by hydrazine and in the final properties of the materials. Ni/carbon catalysts could store significant amounts of hydrogen at room temperature and high pressure (0.53%/30 bars), probably through the hydrogen spillover effect. (author)

Nickel catalysts for internal reforming in molten carbonate fuel cells

NARCIS (Netherlands)

Berger, R.J.; Berger, R.J.; Doesburg, E.B.M.; Doesburg, E.B.M.; van Ommen, J.G.; Ross, J.R.H.; Ross, J.R.H.

1996-01-01

Natural gas may be used instead of hydrogen as fuel for the molten carbonate fuel cell (MCFC) by steam reforming the natural gas inside the MCFC, using a nickel catalyst (internal reforming). The severe conditions inside the MCFC, however, require that the catalyst has a very high stability. In

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.

A submerged ceramic membrane reactor for the p-nitrophenol hydrogenation over nano-sized nickel catalysts.

Science.gov (United States)

Chen, R Z; Sun, H L; Xing, W H; Jin, W Q; Xu, N P

2009-02-01

The catalytic hydrogenation of p-nitrophenol to p-aminophenol over nano-sized nickel catalysts was carried out in a submerged ceramic membrane reactor. It has been demonstrated that the submerged ceramic membrane reactor is more suitable for the p-nitrophenol hydrogenation over nano-sized nickel catalysts compared with the side-stream ceramic membrane reactor, and the membrane module configuration has a great influence on the reaction rate of p-nitrophenol hydrogenation and the membrane treating capacity. The deactivation of nano-sized nickel is mainly caused by the adsorption of impurity on the surface of nickel and the increase of oxidation degree of nickel.

Stability, carbon resistance, and reactivity toward autothermal reforming of nickel on ceria-based supports

International Nuclear Information System (INIS)

Sutthisripok, W.; Laosiripojana, N.

2004-01-01

'Full text:' Solid Oxide Fuel Cell (SOFC) normally requires a reformer unit, where the fuel such as natural gas, methane, methanol, or ethanol can be reformed to hydrogen before introducing to the main part of fuel cell. Nickel on commercial supports such as Al2O3, MgO, ZrO2 has been widely reported to be used as the reforming catalyst commercially. Carbon formation and catalyst deactivation are always the main problems of using this type of catalyst. It is well established that CeO2 and CeO2-ZrO2 have been applied as the catalysts in a wide variety of reactions involving oxidation or partial oxidation of hydrocarbons (e.g. automotive catalysis). In order to quantify the performance of nickel on CeO2 and CeO2-ZrO2 supports for reformer application, the stabilities toward methane steam reforming and the carbon formation resistance were studied. After 18 hours, nickel on CeO2-ZrO2 with the Ce/Zr ratio of 3/1 presented the best performance in term of stability and activity. It also provided excellent resistance toward carbon formation compared to commercial Ni/Al2O3. The autothermal reforming of methane over Ni catalyst on CeO2 and CeO2-ZrO2 supports were also investigated. Ni/Ce-ZrO2 with the Ce/ Zr ratio of 3/1 also showed the best performance. The kinetics of this reaction was also studied. In the temperature range of 750-900C, the reaction order in methane was always closed to 1. The catalyst showed a slight positive effect of hydrogen and a negative effect of steam on the steam reforming rate. The addition of oxygen increased the steam reforming rate. However, the productions of CO and H2 decreased with increasing oxygen partial pressure. (author)

A nanostructural study of Raney-type nickel catalysts

NARCIS (Netherlands)

Devred, F.

2004-01-01

Raney-type nickel catalysts have been applied in commercial hydrogenation reactions for decades. They are relatively cheap and have proven to be very efficient in hydrogenation. The preparation process is relatively simple, but it appears that many parameters have an influence on the performance of

Electroless Nickel-Based Catalyst for Diffusion Limited Hydrogen Generation through Hydrolysis of Borohydride

Directory of Open Access Journals (Sweden)

Shannon P. Anderson

2013-07-01

Full Text Available Catalysts based on electroless nickel and bi-metallic nickel-molybdenum nanoparticles were synthesized for the hydrolysis of sodium borohydride for hydrogen generation. The catalysts were synthesized by polymer-stabilized Pd nanoparticle-catalyzation and activation of Al2O3 substrate and electroless Ni or Ni-Mo plating of the substrate for selected time lengths. Catalytic activity of the synthesized catalysts was tested for the hydrolyzation of alkaline-stabilized NaBH4 solution for hydrogen generation. The effects of electroless plating time lengths, temperature and NaBH4 concentration on hydrogen generation rates were analyzed and discussed. Compositional analysis and surface morphology were carried out for nano-metallized Al2O3 using Scanning Electron Micrographs (SEM and Energy Dispersive X-Ray Microanalysis (EDAX. The as-plated polymer-stabilized electroless nickel catalyst plated for 10 min and unstirred in the hydrolysis reaction exhibited appreciable catalytic activity for hydrolysis of NaBH4. For a zero-order reaction assumption, activation energy of hydrogen generation using the catalyst was estimated at 104.6 kJ/mol. Suggestions are provided for further work needed prior to using the catalyst for portable hydrogen generation from aqueous alkaline-stabilized NaBH4 solution for fuel cells.

HDS, HDN and HDA activities of nickel-molybdenum catalysts supported on alumina

Energy Technology Data Exchange (ETDEWEB)

Dominguez-Crespo, M.A. [Instituto Mexicano del Petroleo, Programa de Tratamiento de Crudo Maya. Avenida Eje Central Lazaro Cardenas No.152, Col. San Bartolo Atepehuacan, 07730, Mexico D. F. (Mexico); Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada (CICATA-Altamira, IPN) Km 14.5 Carretera Tampico-puerto Industrial 89600, Altamira, Tamaulipas (Mexico); Torres-Huerta, A.M.; Ramirez-Meneses, E. [Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada (CICATA-Altamira, IPN) Km 14.5 Carretera Tampico-puerto Industrial 89600, Altamira, Tamaulipas (Mexico); Diaz-Garcia, L. [Instituto Mexicano del Petroleo, Programa de Tratamiento de Crudo Maya. Avenida Eje Central Lazaro Cardenas No.152, Col. San Bartolo Atepehuacan, 07730, Mexico D. F. (Mexico); Arce-Estrada, E.M. [Instituto Politecnico Nacional, Departamento de Metalurgia y Materiales. A.P. 75-876, 07300 Mexico, D. F. (Mexico)

2008-08-15

In this work, NiMo-Al{sub 2}O{sub 3} catalysts were prepared by using different alumina precursors. The supports were impregnated by means of the spray at incipient wetness technique in both basic and acid media. Both the supports and fresh catalysts were characterized by the adsorption-desorption isotherms, Temperature-Programmed Reduction (TPR), Thermal Pyridine Adsorption-Desorption (TPD) and X-Ray Diffraction analyses (XRD). After sulfidation, the NiMoS metallic particles were characterized by Transmission Electron Microscopy (TEM). The initial analyses were performed in a trickle-bed reactor by using a real feedstock (Mexican heavy gas oil) and performing hydrotreating reactions (HDS, HDN and HDA) at three different temperatures: 613, 633 and 653 K; and 54 kg cm{sup -} {sup 2}. The catalytic activities are discussed in relation to the physicochemical properties of the NiMo catalysts, alumina phase and pH of the impregnating solution. The catalytic results show an increase in the conversion profiles with temperature. The sulfur conversion was increased from 89 to 99.25%, 91-99%, 90.8-97%, 83-95% and 78-96% when the crystal size of the support varied from 3 to 20 nm, respectively. The nitrogen and aromatic conversions were also increased in the range of 23-45 wt.%. It was found that the {gamma} phase reached a higher catalytic performance than the {eta} phase. The NiMo catalysts synthesized in a basic medium showed a better catalytic performance than that obtained with those prepared in acid solutions. The significance of the kinetic data to compare the catalysts is discussed. The maximum value of the catalytic activity was reached with the catalysts with the smallest particle sizes. (author)

Synthesis of Single-Walled Carbon Nanotubes: Effects of Active Metals, Catalyst Supports, and Metal Loading Percentage

Directory of Open Access Journals (Sweden)

Wei-Wen Liu

2013-01-01

Full Text Available The effects of active metals, catalyst supports, and metal loading percentage on the formation of single-walled carbon nanotubes (SWNTs were studied. In particular, iron, cobalt, and nickel were investigated for SWNTs synthesis. Iron was found to grow better-quality SWNTs compared to cobalt and nickel. To study the effect of catalyst supports, magnesium oxide, silicon oxide, and aluminium oxide were chosen for iron. Among the studied supports, MgO was identified to be a suitable support for iron as it produced SWNTs with better graphitisation determined by Raman analysis. Increasing the iron loading decreased the quality of SWNTs due to extensive agglomeration of the iron particles. Thus, lower metal loading percentage is preferred to grow better-quality SWNTs with uniform diameters.

Deoxygenation of methyl laurate over Ni based catalysts: Influence of supports

Science.gov (United States)

Xia, Xiaoqiang; Chen, Hui; Bi, Yadong; Hu, Jianli

2017-10-01

The use of a series of nickel based catalysts supported over HZSM-5, Al2O3, C and ZrO2 in the deoxygenation of methyl laurate shows that the deoxygenation activity and deoxygenation pathway of nickel based catalysts can be affected by properties of catalysts. In the absence of H2, β-elimination of methyl laurate is the dominant reaction and a small amount of laurate acid is converted into undecane by direct decarboxylation. At the same time, the highly acidic support HZSM-5 gave higher conversion and C11 alkane selectivity. In the presence of H2, Ni/HZSM-5 catalyst showed a significantly high deoxygenation activity, producing 71% alkanes by methyl laurate conversion at 280 °C and 4MPa H2. While as on mildly acidic (Al2O3) and neutral (C) supports, a restricted hydrodeoxygenation activity was achieved but more oxygenate products were yielded. According to the analysis of intermediate product, the deoxygenation reaction of methyl laurate follows three distinct pathways: in the absence of H2, decarboxylation: C11H23COOCH3→C11H23COOH→C11H24; in the presence of H2, decarbonylation: C11H23COOCH3→C11H23COOH→C11H23CHO→C11H24; and hydrodeoxygenation: C11H23COOCH3 →C11H23COOH→C11H23CHO→C12H25OH→C12H26

Ni/SiO2 Catalyst Prepared with Nickel Nitrate Precursor for Combination of CO2 Reforming and Partial Oxidation of Methane: Characterization and Deactivation Mechanism Investigation

Directory of Open Access Journals (Sweden)

Sufang He

2015-01-01

Full Text Available The performance of Ni/SiO2 catalyst in the process of combination of CO2 reforming and partial oxidation of methane to produce syngas was studied. The Ni/SiO2 catalysts were prepared by using incipient wetness impregnation method with nickel nitrate as a precursor and characterized by FT-IR, TG-DTA, UV-Raman, XRD, TEM, and H2-TPR. The metal nickel particles with the average size of 37.5 nm were highly dispersed over the catalyst, while the interaction between nickel particles and SiO2 support is relatively weak. The weak NiO-SiO2 interaction disappeared after repeating oxidation-reduction-oxidation in the fluidized bed reactor at 700°C, which resulted in the sintering of metal nickel particles. As a result, a rapid deactivation of the Ni/SiO2 catalysts was observed in 2.5 h reaction on stream.

Nanosheet Supported Single-Metal Atom Bifunctional Catalyst for Overall Water Splitting.

Science.gov (United States)

Ling, Chongyi; Shi, Li; Ouyang, Yixin; Zeng, Xiao Cheng; Wang, Jinlan

2017-08-09

Nanosheet supported single-atom catalysts (SACs) can make full use of metal atoms and yet entail high selectivity and activity, and bifunctional catalysts can enable higher performance while lowering the cost than two separate unifunctional catalysts. Supported single-atom bifunctional catalysts are therefore of great economic interest and scientific importance. Here, on the basis of first-principles computations, we report a design of the first single-atom bifunctional eletrocatalyst, namely, isolated nickel atom supported on β 12 boron monolayer (Ni 1 /β 12 -BM), to achieve overall water splitting. This nanosheet supported SAC exhibits remarkable electrocatalytic performance with the computed overpotential for oxygen/hydrogen evolution reaction being just 0.40/0.06 V. The ab initio molecular dynamics simulation shows that the SAC can survive up to 800 K elevated temperature, while enacting a high energy barrier of 1.68 eV to prevent isolated Ni atoms from clustering. A viable experimental route for the synthesis of Ni 1 /β 12 -BM SAC is demonstrated from computer simulation. The desired nanosheet supported single-atom bifunctional catalysts not only show great potential for achieving overall water splitting but also offer cost-effective opportunities for advancing clean energy technology.

Ni-SiO2 Catalysts for the Carbon Dioxide Reforming of Methane: Varying Support Properties by Flame Spray Pyrolysis

Directory of Open Access Journals (Sweden)

Emma C. Lovell

2015-03-01

Full Text Available Silica particles were prepared by flame spray pyrolysis (FSP as a support for nickel catalysts. The impact of precursor feed rate (3, 5 and 7 mL/min during FSP on the silica characteristics and the ensuing effect on catalytic performance for the carbon dioxide, or dry, reforming of methane (DRM was probed. Increasing the precursor feed rate: (i progressively lowered the silica surface area from ≈340 m2/g to ≈240 m2/g; (ii altered the silanol groups on the silica surface; and (iii introduced residual carbon-based surface species to the sample at the highest feed rate. The variations in silica properties altered the (5 wt % nickel deposit characteristics which in turn impacted on the DRM reaction. As the silica surface area increased, the nickel dispersion increased which improved catalyst performance. The residual carbon-based species also appeared to improve nickel dispersion, and in turn catalyst activity, although not to the same extent as the change in silica surface area. The findings illustrate both the importance of silica support characteristics on the catalytic performance of nickel for the DRM reaction and the capacity for using FSP to control these characteristics.

Aqueous processing of nickel spent catalyst for a value added product

International Nuclear Information System (INIS)

Sheik, Abdul Rauf; Ghosh, Malay Kumar; Sanjay, Kali; Subbaiah, Tondepu; Mishra, Barada Kanta; Baba, Abdullahi Aalafara

2013-01-01

Nickel was recovered from a fertilizer industry spent catalyst by leaching with nitric acid followed by nickel hydroxide precipitation. The optimization of temperature, initial acid concentration and particle size for leaching of the spent catalyst was done through 2 3 factorial design. A maximum extraction of 91.9% was achieved at 90 .deg. C, 1.5M HNO 3 and 62.5 µm particle size. Temperature and acid concentration showed positive effect, while particle size showed no effect. A regression equation was developed and employed to predict conditions for 100% extraction which were experimentally tested. Nickel hydroxide was electrochemically precipitated from the leach liquor and its maximum discharge capacity was found to be 155 mAh/g. A 3-stage counter current leaching circuit was designed to obtain a leach liquor of suitable pH. XRD characterization of the precipitated Ni(OH) 2 shows to consist of both α- and β-forms

An anodic alumina supported Ni-Pt bimetallic plate-type catalysts for multi-reforming of methane, kerosene and ethanol

KAUST Repository

Zhou, Lu

2014-05-01

An anodic alumina supported Ni-Pt bimetallic plate-type catalyst was prepared by a two-step impregnation method. The trace amount 0.08 wt% of Pt doping efficiently suppressed the nickel particle sintering and improved the nickel oxides reducibility. The prepared Ni-Pt catalyst showed excellent performance during steam reforming of methane, kerosene and ethanol under both 3000 h stationary and 500-time daily start-up and shut-down operation modes. Self-activation ability of this catalyst was evidenced, which was considered to be resulted from the hydrogen spillover effect over Ni-Pt alloy. In addition, an integrated combustion-reforming reactor was proposed in this study. However, the sintering of the alumina support is still a critical issue for the industrialization of Ni-Pt catalyst. Copyright © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

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

NARCIS (Netherlands)

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

1992-01-01

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

TiO2 nanotubes supported NiW hydrodesulphurization catalysts: Characterization and activity

International Nuclear Information System (INIS)

Palcheva, R.; Dimitrov, L.; Tyuliev, G.; Spojakina, A.; Jiratova, K.

2013-01-01

Highlights: ► NiW catalysts supported on TiO 2 nanotubes, titania and alumina. ► The best results are obtained with NiW/TiO 2 nanotubes in hydrodesulfurization (HDS) of thiophene. ► Active phase is Ni-WO x S y . ► Electronic promotion of W by Ti. - Abstract: High surface area TiO 2 nanotubes (Ti-NT) synthesized by alkali hydrothermal method were used as a support for NiW hydrodesulphurization catalyst. Nickel salt of 12-tungstophosphoric acid – Ni 3/2 PW 12 O 40 was applied as oxide precursor of the active components. The catalyst was characterized by S BET , XRD, UV–vis DRS, Raman spectroscopy, XPS, TPR and HRTEM. The results obtained were compared with those for the NiW catalysts prepared over high surface area titania and alumina supports. A polytungstate phase evidenced by Raman spectroscopy was observed indicating the destruction of the initial heteropolyanion. The catalytic experiments revealed two times higher thiophene conversion on NiW catalyst supported on Ti-NT than those of catalysts supported on alumina and titania. Increased HDS activity of the NiW catalyst supported on Ti-NT could be related to a higher amount of W oxysulfide entities interacting with Ni sulfide particles as consequence of the electronic effects of the Ti-NT observed with XPS analysis.

Development and characterization of nickel catalysts supported in CeO2-ZrO2-Al2O3, CeO2-La2O3-Al2O3 e ZrO2-La2O3-Al2O3 matrixes evaluated for methane reforming reactions

International Nuclear Information System (INIS)

Abreu, Amanda Jordão de

2012-01-01

Nowadays, the methane reforming is large interest industrial for the take advantage of these gas in production the hydrogen and synthesis gas (syngas). Among in the reactions of methane stand of the reactions steam reforming and carbon dioxide reforming of methane. The main catalysts uses in the methane reforming is Ni/Al 2 O 3 . However, the supported-nickel catalyst is susceptible to the deactivation or the destruction by coke deposition. The carbon dissolves in the nickel crystallite and its diffuses through the nickel, leading for formation of the carbon whiskers, which results in fragmentation of the catalyst. Modification of such catalysts, like incorporation of suitable promoters, is desirable to achieve reduction of the methane hydrogenolysis and/or promotion of the carbon gasification. Catalysts 5%Ni/Al 2 O 3 supported on solid solutions formed by ZrO 2 -CeO 2 , La 2 O 3 and CeO 2 -ZrO 2 -La 2 O 3 were prepared, characterized and evaluated in reactions steam and carbon dioxide reforming and partial oxidation of methane with objective the value effect loading solution solid in support. The supports were prepared by co-precipitation method and catalysts were prepared by impregnation method and calcined at 500 deg C. The supports and catalysts were characterized by Nitrogen Adsorption, method -rays diffraction (XRD), X-rays dispersive spectroscopy (XDS), spectroscopy in the region of the ultraviolet and the visible (UV-vis NIR) to and temperature programmed reduction (TPR), Raman Spectroscopy, X-ray absorption spectroscopy and Thermogravimetric Analysis. After all the catalytic reactions check which the addition of solid solution is beneficial for Ni/Al 2 O 3 catalysts and the best catalysts are Ni/CeO 2 -La 2 O 3 -Al 2 O 3 . (author)

Co, Fe and Ni catalysts supported on coke for direct coal liquefaction

International Nuclear Information System (INIS)

Jimenez, Jose A; Villalba, Oscar A; Rodriguez, Luis I; Hernandez, Orlando; Agamez, Yasmin Y; Dias Jose de Jesus

2008-01-01

Transition metal catalysts supported on coke were prepared by impregnation with a solution of complex of metal-thiourea, that is produced from salt precursors of cobalt chloride, Nickel chloride or iron sulfate and ammonium. sulphide formation on the support surface was generated by decomposition of the metal complex. The catalysts obtained were used in direct coal liquefaction of a medium volatile bituminous coal (Yerbabuena N 1) from Cundinamarca using a 250 Ml, Parr reactor at 723 K and a hydrogen-donor solvent. The catalytic results show, for all samples, both a good coal conversion and an enhancement of the yield of oils, this indicates that the proposed preparation method of catalyst is effective and that eventually the H 2 S sulphidation conventional process could be replaced

[Spectralsignatures of nickel and vanadium supported photocatalysts and their photocatalytic properties].

Science.gov (United States)

Hai, Feng; Zhang, Qian-Cheng; Wang, Zhi-Wei; Jian, Li

2011-04-01

Using SiO2, activated carbon (AC) and Al2O3 as supports, the supported photocatalysts Ni-V-O/SiO2, Ni-V-O/AC and Ni-V-O/Al2O3 were prepared by impregnation method, and their spectralsignatures were investigated. The carbonylation of methanol with CO2 under UV irradiation was used as a probe reaction to compare the photocatalytic performance of the prepared catalysts. Integrated with the testing results of carbonylation, the effects of different supports on selectivity for the carbonylation products of methyl formate (MF) and dimethyl carbonate (DMC) were discussed by pyridine-IR and UV-Vis techniques. XRD results showed that the particles of nickel and vanadium supported on SiO2 had the highest degree of dispersion. Results of pyridine-IR indicated that all catalysts retained Lewis acid sites. The acid strength was different from catalyst samples with different supports but with the same active components. The acid strengths could be arranged as follows: Ni-V-O/SiO2 > Ni-V-O/Al2 O3 > Ni-V-O/AC. Different acid strengths exhibited different influence on the selectivity of products MF and DMC of carbonylation. The surface acid strengths of catalysts were the major factor influencing the selectivity of carbonylation products.

Hydrogen Production by Steam Reforming of Natural Gas Over Vanadium-Nickel-Alumina Catalysts.

Science.gov (United States)

Yoo, Jaekyeong; Park, Seungwon; Song, Ji Hwan; Song, In Kyu

2018-09-01

A series of vanadium-nickel-alumina (xVNA) catalysts were prepared by a single-step sol-gel method with a variation of vanadium content (x, wt%) for use in the hydrogen production by steam reforming of natural gas. The effect of vanadium content on the physicochemical properties and catalytic activities of xVNA catalysts in the steam reforming of natural gas was investigated. It was found that natural gas conversion and hydrogen yield showed volcano-shaped trends with respect to vanadium content. It was also revealed that natural gas conversion and hydrogen yield increased with decreasing nickel crystallite size.

CONVERSION OF (±-CITRONELLAL AND ITS DERIVATIVES TO (--MENTHOL USING BIFUNCTIONAL NICKEL ZEOLITE CATALYSTS

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Indri Badria Adilina

2015-06-01

Full Text Available (±-Citronellal and its derivatives were converted to (--menthol by a one-pot reaction system using zeolite based nickel catalysts. The catalysts were prepared by immobilization of nickel on natural zeolite (NZ or synthetic zeolite (ZSM-5 by a simple cation exchange method. Calcination and hydrogen treatment procedures were able to significantly increase the surface area and pore volume of NZ based catalysts whereas negligible changes in the properties were observed for that of ZSM-5. Catalytic reactions were carried out at 70ºC by stirring the mixture in the air for cyclization of (±-citronellal to (±-isopulegol followed by hydrogenation towards the desired (--menthol at 2 Mpa of H2 pressure. The Ni/NZ catalyst was able to convert a (±-citronellal derivative yielding 9% (--menthol (36% selectivity with conversion up to 24%, whereas Ni/ZSM5 catalyst directly converted 65% (±-citronellal to give 4% menthol (6% selectivity. These zeolite based catalysts are therefore potential materials for the conversion of biomass feed stock to value-added chemicals.

Nitrogen-Doped Carbon Encapsulated Nickel/Cobalt Nanoparticle Catalysts for Olefin Migration of Allylarenes

DEFF Research Database (Denmark)

Kramer, Søren; Mielby, Jerrik Jørgen; Buss, Kasper Spanggård

2017-01-01

Olefin migration of allylarenes is typically performed with precious metal-based homogeneous catalysts. In contrast, very limited progress has been made using cheap, earth-abundant base metals as heterogeneous catalysts for these transformations - in spite of the obvious economic and environmental...... advantages. Herein, we report on the use of an easily prepared heterogeneous catalyst material for the migration of olefins, in particular allylarenes. The catalyst material consists of nickel/cobalt alloy nanoparticles encapsulated in nitrogen-doped carbon shells. The encapsulated nanoparticles are stable...

METHANE STEAM REACTION OVER NICKEL CATALYSTS IN THE HYNOL PROCESS

Science.gov (United States)

The report discusses the reaction of methane-steam over nickel catalysts in the Hynol process, a process that uses biomass and natural gas as feedstocks to maximize methanol yields and minimize greenhouse gas emissions. EPA's APPCD has established a laboratory in which to conduct...

Stereoselective hydrogenation of H-alkynes on boron-nickel catalysts

International Nuclear Information System (INIS)

Petrova, S.S.; Sijmer, Eh.Kh.; Amitan, I.I.

1992-01-01

It is ascertained that in the course of stereoselective hydrogenation of H-alkynes on boron-nickel catalysts the contact modified by 2-phenyl-1,5 dimethylpyrasol-2-anom in the ratio Ni(2+):BH 4 -=1:5 is the most active and selective one. Moreover, cis-alkane was prepared with the yield of 94.5% and selective of 79%

Pyrolysis-catalysis of waste plastic using a nickel-stainless-steel mesh catalyst for high-value carbon products.

Science.gov (United States)

Zhang, Yeshui; Nahil, Mohamad A; Wu, Chunfei; Williams, Paul T

2017-11-01

A stainless-steel mesh loaded with nickel catalyst was produced and used for the pyrolysis-catalysis of waste high-density polyethylene with the aim of producing high-value carbon products, including carbon nanotubes (CNTs). The catalysis temperature and plastic-to-catalyst ratio were investigated to determine the influence on the formation of different types of carbon deposited on the nickel-stainless-steel mesh catalyst. Increasing temperature from 700 to 900°C resulted in an increase in the carbon deposited on the nickel-loaded stainless-steel mesh catalyst from 32.5 to 38.0 wt%. The increase in sample-to-catalyst ratio reduced the amount of carbon deposited on the mesh catalyst in terms of g carbon g -1 plastic. The carbons were found to be largely composed of filamentous carbons, with negligible disordered (amorphous) carbons. Transmission electron microscopy analysis of the filamentous carbons revealed them to be composed of a large proportion (estimated at ∼40%) multi-walled carbon nanotubes (MWCNTs). The optimum process conditions for CNT production, in terms of yield and graphitic nature, determined by Raman spectroscopy, was catalysis temperature of 800°C and plastic-to-catalyst ratio of 1:2, where a mass of 334 mg of filamentous/MWCNTs g -1 plastic was produced.

Emprego de catalisadores à base de níquel para homo- e copolimerização de estireno The use of nickel-based catalysts for homo-and copolymerization of styrene

Directory of Open Access Journals (Sweden)

Luis Carlos Ferreira Jr.

2004-12-01

Full Text Available This review deals with the homo- and copolymerization of styrene with nickel catalysts. The catalytic activity, polymer stereoregularity, polymer molecular weight and polydispersity are dependent upon nickel ligands and reaction parameters. Catalysts supported on silica, treated with methylaluminoxane (MAO, have shown higher stereospecificity and activity compared to homogeneous ones. The influence of these parameters is discussed focusing on the elucidation of some aspects of the polymerization mechanism.

Influence of supports on catalytic behavior of nickel catalysts in carbon dioxide reforming of toluene as a model compound of tar from biomass gasification.

Science.gov (United States)

Kong, Meng; Fei, Jinhua; Wang, Shuai; Lu, Wen; Zheng, Xiaoming

2011-01-01

A series of supported Ni catalysts including Ni/MgO, Ni/γ-Al2O3, Ni/α-Al2O3, Ni/SiO2 and Ni/ZrO2 was tested in CO2 reforming of toluene as a model compound of tar from biomass gasification in a fluidized bed reactor, and characterized by the means of temperature programmed reduction with hydrogen (H2-TPR), XRD, TEM and temperature programmed oxidation (TPO). Combining the characterization results with the performance tests, the activity of catalyst greatly depended on Ni particles size, and the stability was affected by the coke composition. Both of them (Ni particle size and coke composition) were closely related to the interaction between nickel and support which would determine the chemical environment where Ni inhabited. The best catalytic performance was observed on Ni/MgO due to the strong interaction between NiO and MgO via the formation of Ni-Mg-O solid solution, and the highest dispersion of Ni particle in the basic environment. Copyright © 2010 Elsevier Ltd. All rights reserved.

Hydrogen production with nickel powder cathode catalysts in microbial electrolysis cells

KAUST Repository

Selembo, Priscilla A.

2010-01-01

Although platinum is commonly used as catalyst on the cathode in microbial electrolysis cells (MEC), non-precious metal alternatives are needed to reduce costs. Cathodes were constructed using a nickel powder (0.5-1 μm) and their performance was compared to conventional electrodes containing Pt (0.002 μm) in MECs and electrochemical tests. The MEC performance in terms of coulombic efficiency, cathodic, hydrogen and energy recoveries were similar using Ni or Pt cathodes, although the maximum hydrogen production rate (Q) was slightly lower for Ni (Q = 1.2-1.3 m3 H2/m3/d; 0.6 V applied) than Pt (1.6 m3 H2/m3/d). Nickel dissolution was minimized by replacing medium in the reactor under anoxic conditions. The stability of the Ni particles was confirmed by examining the cathodes after 12 MEC cycles using scanning electron microscopy and linear sweep voltammetry. Analysis of the anodic communities in these reactors revealed dominant populations of Geobacter sulfurreduces and Pelobacter propionicus. These results demonstrate that nickel powder can be used as a viable alternative to Pt in MECs, allowing large scale production of cathodes with similar performance to systems that use precious metal catalysts. © 2009 Professor T. Nejat Veziroglu.

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

The effect of Ni-Al ratio on the properties of coprecipitated nickel-alumina catalysts with high nickel contents

NARCIS (Netherlands)

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

1986-01-01

A series of nickel-alumina catalysts with a Ni/Al ratio between 3 and 20 has been prepared by coprecipitation. The calcination and reduction of these samples have been studied by thermogravimetry and their structures after calcination and reduction at different temperatures has been examined by

Wet chemical synthesis of nickel supported on alumina catalysts; Sintese de catalisadores de niquel suportado em alumina por via umida

Energy Technology Data Exchange (ETDEWEB)

Freire, Ranny Rodrigues; Costa, Talita Kenya Oliveira; Morais, Ana Carla da Fonseca Ferreira; Costa, Ana Cristina Figueiredo de Melo; Freitas, Normanda Lino de, E-mail: normanda@ufcg.edu.br [Universidade Federal de Campina Grande (UFCG), PB (Brazil)

2016-07-01

Heterogenic catalysts are those found to be in a different phase on the reaction when compared to the reactants and products. Preferred when compared to homogeneous catalysts due to the easiness on which the separation is processed. The objective of this study is to obtain and characterize Alumina based catalysts impregnated with Nickel (Al{sub 2}O{sub 3}), by wet impregnation. The alumina was synthesized by combustion reaction. Before and after the impregnation the catalysts were characterized by X-ray diffraction (XRD), granulometric analysis, the textural analysis will be held by nitrogen adsorption (BET), energy-dispersive X-ray spectroscopy (EDX) and scanning electron microscopy (SEM). The results show a presence of a stable crystalline phase of Al2O3 in all the studied samples and after the impregnation the second phase formed was of NiO and NiAl{sub 2}O{sub 4}. The Al{sub 2}O{sub 3} e Ni/Al{sub 2}O{sub 3} catalysts resulted in clusters with a medium diameter of 18.9 and 14.2 μm, respectively. The catalysts show a medium-pore characteristic (medium pore diameter between 2 and 50 nm), the superficial area to Al{sub 2}O{sub 3} and Ni/Al{sub 2}O{sub 3} catalysts were 8.69 m{sup 2}/g and 5.56 m{sup 2}/g, respectively. (author)

Carbon-Nanotube-Supported Bio-Inspired Nickel Catalyst and Its Integration in Hybrid Hydrogen/Air Fuel Cells

Energy Technology Data Exchange (ETDEWEB)

Gentil, Solène [Univ. Grenoble Alpes, CNRS, DCM UMR 5250, 38000 Grenoble France; Laboratoire de Chimie et Biologie des Métaux, Univ. Grenoble Alpes, CNRS UMR5249, CEA, 38000 Grenoble France; Lalaoui, Noémie [Univ. Grenoble Alpes, CNRS, DCM UMR 5250, 38000 Grenoble France; Dutta, Arnab [Pacific Northwest National Laboratory, Richland WA 99532 USA; Current address: Chemistry Department, IIT Gandhinagar, Gujarat 382355 India; Nedellec, Yannig [Univ. Grenoble Alpes, CNRS, DCM UMR 5250, 38000 Grenoble France; Cosnier, Serge [Univ. Grenoble Alpes, CNRS, DCM UMR 5250, 38000 Grenoble France; Shaw, Wendy J. [Pacific Northwest National Laboratory, Richland WA 99532 USA; Artero, Vincent [Laboratoire de Chimie et Biologie des Métaux, Univ. Grenoble Alpes, CNRS UMR5249, CEA, 38000 Grenoble France; Le Goff, Alan [Univ. Grenoble Alpes, CNRS, DCM UMR 5250, 38000 Grenoble France

2017-01-12

A biomimetic nickel bis-diphosphine complex incorporating the amino-acid arginine in the outer coordination sphere, was immobilized on modified single-wall carbon nanotubes (SWCNTs) through electrostatic interactions. The sur-face-confined catalyst is characterized by a reversible 2-electron/2-proton redox process at potentials close to the equibrium potential of the H+/H2 couple. Consequently, the functionalized redox nanomaterial exhibits reversible electrocatalytic activity for the H2/2H+ interconversion over a broad range of pH. This system exhibits catalytic bias, analogous to hydrogenases, resulting in high turnover frequencies at low overpotentials for electrocatalytic H2 oxida-tion between pH 0 and 7. This allowed integrating such bio-inspired nanomaterial together with a multicopper oxi-dase at the cathode side in a hybrid bioinspired/enzymatic hydrogen fuel cell. This device delivers ~2 mW cm–2 with an open-circuit voltage of 1.0 V at room temperature and pH 5, which sets a new efficiency record for a bio-related hydrogen fuel cell with base metal catalysts.

Conversion of Methane into Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor

Energy Technology Data Exchange (ETDEWEB)

Okolie, Chukwuemeka [School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW Atlanta GA 30332 USA; Belhseine, Yasmeen F. [School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW Atlanta GA 30332 USA; Lyu, Yimeng [School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW Atlanta GA 30332 USA; Yung, Matthew M. [National Renewable Energy Laboratory, Golden CO 80401 USA; Engelhard, Mark H. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Lab, Richland WA 99354 USA; Kovarik, Libor [Environmental Molecular Sciences Laboratory, Pacific Northwest National Lab, Richland WA 99354 USA; Stavitski, Eli [National Synchrotron Light Source II, Brookhaven National Laboratory, Upton NY 11973 USA; Sievers, Carsten [School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW Atlanta GA 30332 USA

2017-09-26

Direct conversion of methane into alcohols is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can selectively oxidize methane to methanol and ethanol in a single, steady-state process at 723 K using O2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to the synergy between the small Lewis acidic NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.

Decomposition of hydrogen peroxide on nickel oxide - vanadium pentoxide catalysts and the effect of ionizing radiation on them

International Nuclear Information System (INIS)

Mucka, V.

1984-01-01

Some physico-chemical and catalytic properties of nickel oxide-vanadium pentoxide two-component catalysts were studied over the entire concentration range of the components, using the decomposition of hydrogen peroxide in an aqueous solution as the test reaction. The two oxides were found to affect each other; this was shown by the dependences of the specific surface area, the V 4+ ion concentration, and the catalyst activity on the system composition. At low vanadium pentoxide concentrations (up to 15 mol%) the reaction took place on nickel oxide modified with vanadium pentoxide, whereas in the region of higher vanadium pentoxide concentrations the decomposition of the peroxide was catalyzed primarily in the homogeneous phase by vanadium(V) peroxide ions; in a sample with 30 mol% V 2 O 5 , trivalent vanadium also played a part. With catalysts obtained by mere mechanical mixing of the two oxides, a modified activity was observed in the region of high excess of nickel oxide. The activity of catalyst, particularly pure nickel oxide, was increased by its partial reduction and decreased by its exposure to gamma radiation if the dose was higher than 10 5 Gy. The effects observed are interpreted in terms of the concept of bivalent catalytic centres. (author)

Catalytic performance and characterization of cobalt-nickel nano catalysts for CO hydrogenation

International Nuclear Information System (INIS)

Feyzi, Mostafa; Gholivand, Mohammad Bagher; Babakhanian, Arash

2014-01-01

A series of Co-Ni nano catalysts were prepared by co-precipitation method. We investigated the effect of Co/Ni molar ratios precipitate and calcination conditions on the catalytic performance of cobalt nickel catalysts for Fisher-Tropsch synthesis (FTS). The catalyst containing 90%Co/10%Ni was found to be optimal for the conversion of synthesis gas to light olefins. The activity and selectivity of the optimal catalyst were studied in different operational conditions. The results show that the best operational conditions are the H 2 /CO=2/1 molar feed ratio at 310 .deg. C and GHSV=1,200 h - 1 under 5 bar of pressure. The prepared catalysts were characterized by powder X-ray diffraction (XRD), N 2 adsorption-desorption measurements such as BET and BJH methods, transmission electron microscopy (TEM) and thermal gravimetric analysis (TGA)

Oxidative-reforming of model biogas over NiO/Al{sub 2}O{sub 3} catalysts: The influence of the variation of support synthesis conditions

Energy Technology Data Exchange (ETDEWEB)

Asencios, Yvan J.O., E-mail: yvan.jesus@unifesp.br [Departamento de Ciências do Mar, Universidade Federal de São Paulo, Av. Alm. Saldanha da Gama, 89, Ponta da Praia, CEP: 11030-400, Santos-SP (Brazil); Elias, Kariny F.M. [Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador Sãocarlense, 400, 13560-970, São Carlos-SP (Brazil); Assaf, Elisabete M., E-mail: eassaf@iqsc.usp.br [Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador Sãocarlense, 400, 13560-970, São Carlos-SP (Brazil)

2014-10-30

Graphical abstract: - Highlights: • Precipitation pH and ageing T °C of Al{sub 2}O{sub 3} influenced the performance of Ni/Al{sub 2}O{sub 3}. • Ni catalysts supported on Al{sub 2}O{sub 3} obtained at pH 7 recorded high conversion values. • Catalysts supported on Al{sub 2}O{sub 3} obtained at pH 7 and 80 °C are promissory for reforming of biogas. • Catalysts supported on Al{sub 2}O{sub 3} obtained at pH 6 deactivated readily during reaction. - Abstract: In this study, nickel catalysts (20 wt%) supported on γ-Al{sub 2}O{sub 3} were prepared by the impregnation method. The γ-Al{sub 2}O{sub 3}, was synthesized by precipitation of bayerite gel obtained from aluminum scrap. The synthetic conditions of the bayerite gel varied as follows: precipitation pH ranging from 6 to 7; ageing temperature ranging from 25 to 80 °C, the calcination temperature for all samples was 500 °C. The catalysts and the supports were analyzed by temperature programmed reduction (H{sub 2}-TPR), X-ray diffraction (XRD), physisorption of N{sub 2} (BET), X-ray absorption near-edge structure (XANES) and scanning electron microscopy (SEM). Isopropanol decomposition reactions over the catalysts were carried out to evaluate their acidity. SEM images of the spent catalysts showed that the morphology of the carbon formed during the reaction is of the filamentous type. The TPR analysis of the catalysts showed the presence of NiO species weakly interacted with the support as well as stoichiometric and non-stoichiometric nickel aluminate, the reduction of these species was also observed by XANES analysis. XRD analysis of the fresh catalyst showed peaks assigned to NiO, NiAl{sub 2}O{sub 4} and γ-Al{sub 2}O{sub 3}. The best catalysts (samples NiAl7-25 and NiAl7-80) synthesized in this report showed high stability and high conversion values (CH{sub 4} (70%) and CO{sub 2} (78%)). These catalysts showed better performance than the catalyst supported on commercial γ-Al{sub 2}O{sub 3}, which showed a

Hydrogen Production by Steam Reforming of Liquefied Natural Gas (LNG) Over Nickel-Phosphorus-Alumina Xerogel Catalyst Prepared by a Carbon-Templating Epoxide-Driven Sol-Gel Method.

Science.gov (United States)

Bang, Yongju; Park, Seungwon; Han, Seung Ju; Yoo, Jaekyeong; Choi, Jung Ho; Kang, Tae Hun; Lee, Jinwon; Song, In Kyu

2016-05-01

A nickel-phosphorus-alumina xerogel catalyst was prepared by a carbon-templating epoxide-driven sol-gel method (denoted as CNPA catalyst), and it was applied to the hydrogen production by steam reforming of liquefied natural gas (LNG). For comparison, a nickel-phosphorus-alumina xerogel catalyst was also prepared by a similar method in the absence of carbon template (denoted as NPA catalyst). The effect of carbon template addition on the physicochemical properties and catalytic activities of the catalysts in the steam reforming of LNG was investigated. Both CNPA and NPA catalysts showed excellent textural properties with well-developed mesoporous structure. However, CNPA catalyst retained a more reducible nickel aluminate phase than NPA catalyst. XRD analysis of the reduced CNPA and NPA catalysts revealed that nickel sintering on the CNPA catalyst was suppressed compared to that on the NPA catalyst. From H2-TPD and CH4-TPD measurements of the reduced CNPA and NPA catalysts, it was also revealed that CNPA catalyst with large amount of hydrogen uptake and strong hydrogen-binding sites showed larger amount of methane adsorption than NPA catalyst. In the hydrogen production by steam reforming of LNG, CNPA catalyst with large methane adsorption capacity showed a better catalytic activity than NPA catalyst.

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

Directory of Open Access Journals (Sweden)

Y. J. O. Asencios

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

Gas-phase hydrogenation of benzene on supported nickel catalyst

Energy Technology Data Exchange (ETDEWEB)

Franco, H.A.; Phillips, M.J.

1980-06-01

The reaction of 22.66-280 Pa benzene with 72.39-122.79 Pa hydrogen on kieselguhr-supported nickel at 392.2/sup 0/-468.2/sup 0/K yielded only cyclohexane and was independent of 5.33-40 Pa cyclohexane added to the feed of the differential flow reactor. Best fit for the kinetic data was obtained with a rate equation developed by van Meerten and Coenen which assumed that all hydrogen addition steps have the same rate constant and are slow. An observed rate maximum at 458/sup 0/K may be the result of an increasing rate constant and decreasing cyclohexyl surface coverage as the temperature increases. Temperature-programed hydrogen desorption showed a series of desorption peaks at 358/sup 0/-600/sup 0/K, including one at 453/sup 0/K, which may be due to the hydrogen involved in the surface reaction.

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

International Nuclear Information System (INIS)

Ibrahim, Hussameldin; Idem, Raphael; Aboudheir, Ahmed

2006-01-01

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

Catalytic Fast Pyrolysis of Cellulose by Integrating Dispersed Nickel Catalyst with HZSM-5 Zeolite

Science.gov (United States)

Lei, Xiaojuan; Bi, Yadong; Zhou, Wei; Chen, Hui; Hu, Jianli

2018-01-01

The effect of integrating dispersed nickel catalyst with HZSM-5 zeolite on upgrading of vapors produced from pyrolysis of lignocellulosic biomass was investigated. The active component nickel nitrate was introduced onto the cellulose substrate by impregnation technique. Based on TGA experimental results, we discovered that nickel nitrate first released crystallization water, and then successively decomposed into nickel oxide which was reduced in-situ to metallic nickel through carbothermal reduction reaction. In-situ generated nickel nanoparticles were found highly dispersed over carbon substrate, which were responsible for catalyzing reforming and cracking of tars. In catalytic fast pyrolysis of cellulose, the addition of nickel nitrate caused more char formation at the expense of the yield of the condensable liquid products. In addition, the selectivity of linear oxygenates was increased whereas the yield of laevoglucose was reduced. Oxygen-containing compounds in pyrolysis vapors were deoxygenated into aromatics using HZSM-5. Moreover, the amount of condensable liquid products was decreased with the addition of HZSM-5.

Life Support Catalyst Regeneration Using Ionic Liquids and In Situ Resources

Science.gov (United States)

Abney, Morgan B.; Karr, Laurel; Paley, Mark S.; Donovan, David N.

2016-01-01

Oxygen recovery from metabolic carbon dioxide is an enabling capability for long-duration manned space flight. Complete recovery of oxygen (100%) involves the production of solid carbon. Catalytic approaches for this purpose, such as Bosch technology, have been limited in trade analyses due in part to the mass penalty for high catalyst resupply caused by carbon fouling of the iron or nickel catalyst. In an effort to mitigate this challenge, several technology approaches have been proposed. These approaches have included methods to prolong the life of the catalysts by increasing the total carbon mass loading per mass catalyst, methods for simplified catalyst introduction and removal to limit the resupply container mass, methods of using in situ resources, and methods to regenerate catalyst material. Research and development into these methods is ongoing, but only use of in situ resources and/or complete regeneration of catalyst material has the potential to entirely eliminate the need for resupply. The use of ionic liquids provides an opportunity to combine these methods in a technology approach designed to eliminate the need for resupply of oxygen recovery catalyst. Here we describe the results of an initial feasibility study using ionic liquids and in situ resources for life support catalyst regeneration, we discuss the key challenges with the approach, and we propose future efforts to advance the technology.

Energetic Mapping of Ni Catalysts by Detailed Kinetic Modeling

DEFF Research Database (Denmark)

Bjørgum, Erlend; Chen, De; Bakken, Mari G.

2005-01-01

Temperature-programmed desorption (TPD) of CO has been performed on supported and unsupported nickel catalysts. The unsupported Ni catalyst consists of a Ni(14 13 13) single crystal which has been studied under ultrahigh vacuum conditions. The desorption energy for CO at low CO surface coverage...... was found to be 119 kJ/mol, and the binding energy of C to the Ni(111) surface of the crystal was 703 kJ/mol. The supported catalysts consist of nickel supported on hydrotalcite-like compounds with three different Mg2+/Al3+ ratios. The experimental results show that for the supported Ni catalysts TPD of CO...... precursor seems to result in more steplike sites, kinks, and defects for carbon monoxide dissociation. A detailed kinetic modeling of the TPO results based on elementary reaction steps has been conducted to give an energetic map of supported Ni catalysts. Experimental results from the ideal Ni surface fit...

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.

Hydrogen production by dry reforming of methane with carbon dioxide in one-dimensional nickel-based catalysts; Produccion de hidrogeno mediante el reformado seco de metano con dioxido de carbono en catalizadores unidimensionales a base de niquel

Energy Technology Data Exchange (ETDEWEB)

Lopez U, A. C.

2016-07-01

The main objective of this thesis is development of nickel catalysts supported over 1D matrix of cerium oxide, to be used in dry reforming methane reaction with carbon dioxide for hydrogen production. The catalysts were characterized by: Temperature Programmed Reduction (TPR), Scanning Electronic Microscopy (Sem), Surface Area (Bet method) an X Ray Diffraction (XRD). The TPR technique allowed to define reduction temperature of the active phase in the catalyst, Sem technique showed that the CeO{sub 2} matrix had a nano rod morphology. XRD allowed to identify the crystalline phases of the catalysts. Finally, the catalysts were tested in the dry reforming methane reaction, high catalytic activity and hydrogen production were performed at 700 degrees Celsius and the catalyst with 30 wt.% of nickel. (Author)

Essential elucidation for preparation of supported nickel phosphide upon nickel phosphate precursor

International Nuclear Information System (INIS)

Liu, Xuguang; Xu, Lei; Zhang, Baoquan

2014-01-01

Preparation of supported nickel phosphide (Ni 2 P) depends on nickel phosphate precursor, generally related to its chemical composition and supports. Study of this dependence is essential and meaningful for the preparation of supported Ni 2 P with excellent catalytic activity. The chemical nature of nickel phosphate precursor is revealed by Raman and UV–vis spectra. It is found that initial P/Ni mole ratio ≥0.8 prohibits the Ni-O-Ni bridge bonding (i.e., nickel oxide). This chemical bonding will not result in Ni 2 P structure, verified by XRD characterization results. The alumina (namely, γ-Al 2 O 3 , θ-Al 2 O 3 , or α-Al 2 O 3 ) with distinct physiochemical properties also results in diverse chemical nature of nickel phosphate, and then different nickel phosphides. The influence of alumina support on producing Ni 2 P was explained by the theory of surface energy heterogeneity, calculated by the NLDFT method based on N 2 -sorption isotherm. The uniform surface energy of α-Al 2 O 3 results only in the nickel phosphosate precursor and thus the Ni 2 P phase. - Graphical abstract: Surface energy heterogeneity in alumina (namely α-Al 2 O 3 , θ-Al 2 O 3 , and γ-Al 2 O 3 ) supported multi-oxidic precursors with different reducibilities and thus diverse nickel phosphides (i.e., Ni 3 P, Ni 12 P 5 , Ni 2 P). - Highlights: • Preparing pure Ni 2 P. • Elucidating nickel phosphate precursor. • Associating with surface energy

Effect of SiO 2-ZrO 2 supports prepared by a grafting method on hydrogen production by steam reforming of liquefied natural gas over Ni/SiO 2-ZrO 2 catalysts

Science.gov (United States)

Seo, Jeong Gil; Youn, Min Hye; Song, In Kyu

SiO 2-ZrO 2 supports with various zirconium contents are prepared by grafting a zirconium precursor onto the surface of commercial Carbosil silica. Ni(20 wt.%)/SiO 2-ZrO 2 catalysts are then prepared by an impregnation method, and are applied to hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of SiO 2-ZrO 2 supports on the performance of the Ni(20 wt.%)/SiO 2-ZrO 2 catalysts is investigated. SiO 2-ZrO 2 prepared by a grafting method serves as an efficient support for the nickel catalyst in the steam reforming of LNG. Zirconia enhances the resistance of silica to steam significantly and increases the interaction between nickel and the support, and furthermore, prevents the growth of nickel oxide species during the calcination process through the formation of a ZrO 2-SiO 2 composite structure. The crystalline structures and catalytic activities of the Ni(20 wt.%)/SiO 2-ZrO 2 catalysts are strongly influenced by the amount of zirconium grafted. The conversion of LNG and the yield of hydrogen show volcano-shaped curves with respect to zirconium content. Among the catalysts tested, the Ni(20 wt.%)/SiO 2-ZrO 2 (Zr/Si = 0.54) sample shows the best catalytic performance in terms of both LNG conversion and hydrogen yield. The well-developed and pure tetragonal phase of ZrO 2-SiO 2 (Zr/Si = 0.54) appears to play an important role in the adsorption of steam and subsequent spillover of steam from the support to the active nickel. The small particle size of the metallic nickel in the Ni(20 wt.%)/SiO 2-ZrO 2 (Zr/Si = 0.54) catalyst is also responsible for its high performance.

Preparation and characterization of nickel catalysts supported on cerium for obtaining hydrogen from steam reforming of ethanol; Preparacao e caracterizacao de catalisadores de niquel suportados em ceria para obtencao de hidrogenio a partir da reforma a vapor do etanol

Energy Technology Data Exchange (ETDEWEB)

Urbaninho, A.B.; Bergamaschi, V.S.; Ferreira, J.C., E-mail: jcferrei@ipen.br [Instituto de Pesquisas Energéticas e Nucleares (IPEN/CNEN-SP), São Paulo, SP (Brazil). Centro de Células à Combustível e Hidrogênio

2016-07-01

The Ni/Ce catalysts for were prepared by co- precipitation method with a view to their use in steam reforming of ethanol to produce a hydrogen-rich gas mixture. The catalysts were characterized by scanning electron microscopy; x-ray dispersive Spectroscopy and surface area BET method. This paper proposes to prepare, characterize and test nickel catalyst supported on cerium in order to obtain a material with higher activity and selectivity of the catalyst using the steam reforming reaction of ethanol, by varying the reaction temperature, molar ratio water/ethanol and uptime. The catalytic tests were monitored by chemical analysis of syngas from steam reforming of ethanol using an analysis online by gas Chromatograph in the reactor. (author)

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

Energy Technology Data Exchange (ETDEWEB)

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

2005-09-18

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

Hydrous titanium oxide-supported catalysts

International Nuclear Information System (INIS)

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

1990-01-01

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

Regeneration of Hydrotreating and FCC Catalysts

Energy Technology Data Exchange (ETDEWEB)

CM Wai; JG Frye; JL Fulton; LE Bowman; LJ Silva; MA Gerber

1999-09-30

-earth exchanged Y zeolite in a silica-alumina matrix. X-ray fluorescence analyses showed that the rare earths used in preparing the catalysts were a mixture of lanthanum and cerium. Antimony found in the spent catalyst was added during operation of the FCC unit as a way to suppress the adverse effects of deposited nickel. The fresh HDS samples consisted of sulfided nickel and molybdenum on an alumina support. The spent catalyst showed nearly 10% vanadium on the catalyst and a modest increase in nickel and sulfur on the catalyst as a result of operations. Hydrocracking catalysts were not available for this study.

Oxidation of CO and Methanol on Pd-Ni Catalysts Supported on Different Chemically-Treated Carbon Nanofibers

Directory of Open Access Journals (Sweden)

Juan Carlos Calderón

2016-10-01

Full Text Available In this work, palladium-nickel nanoparticles supported on carbon nanofibers were synthesized, with metal contents close to 25 wt % and Pd:Ni atomic ratios near to 1:2. These catalysts were previously studied in order to determine their activity toward the oxygen reduction reaction. Before the deposition of metals, the carbon nanofibers were chemically treated in order to generate oxygen and nitrogen groups on their surface. Transmission electron microscopy analysis (TEM images revealed particle diameters between 3 and 4 nm, overcoming the sizes observed for the nanoparticles supported on carbon black (catalyst Pd-Ni CB 1:2. From the CO oxidation at different temperatures, the activation energy Eact for this reaction was determined. These values indicated a high tolerance of the catalysts toward the CO poisoning, especially in the case of the catalysts supported on the non-chemically treated carbon nanofibers. On the other hand, apparent activation energy Eap for the methanol oxidation was also determined finding—as a rate determining step—the COads diffusion to the OHads for the catalysts supported on carbon nanofibers. The results here presented showed that the surface functional groups only play a role in the obtaining of lower particle sizes, which is an important factor in the obtaining of low CO oxidation activation energies.

Hydrogenation of citral into its derivatives using heterogeneous catalyst

Science.gov (United States)

Sudiyarmanto, Hidayati, Luthfiana Nurul; Kristiani, Anis; Aulia, Fauzan

2017-11-01

Citral as known as a monoterpene can be found in plants and citrus fruits. The hydrogenation of citral into its derivatives become interesting area for scientist. This compound and its derivatives can be used for many application in pharmaceuticals and food areas. The development of heterogeneous catalysts become an important aspect in catalytic hydrogenation citral process. Nickel supported catalysts are well known as hydrogenation catalyst. These heterogeneous catalysts were tested their catalytic activity in hydrogenation of citral. The effect of various operation conditions, in term of feed concentration, catalyst loading, temperature, and reaction time were also studied. The liquid products produced were analyzed by using Gas Chromatography-Mass Spectroscopy (GC-MS). The result of catalytic activity tests showed nickel skeletal catalyst exhibits best catalytic activity in hydrogenation of citral. The optimum of operation condition was achieved in citral concentration 0.1 M with nickel skeletal catalyst loading of 10% (w/w) at 80 °C and 20 bar for 2 hours produced the highest conversion as of 64.20% and the dominant product resulted was citronellal as of 56.48%.

The effect of titanium nickel nitride decorated carbon nanotubes-reduced graphene oxide hybrid support for methanol oxidation

Science.gov (United States)

Liu, Gen; Pan, Zhanchang; Li, Wuyi; Yu, Ke; Xia, Guowei; Zhao, Qixiang; Shi, Shikun; Hu, Guanghui; Xiao, Chumin; Wei, Zhigang

2017-07-01

Titanium nickel nitride (TiNiN) decorated three-dimensional (3D) carbon nanotubes-reduced graphene oxide (CNT-rGO), a fancy 3D platinum (Pt)-based catalyst hybrid support, is prepared by a solvothermal process followed by a nitriding process, which is tested as anodic catalyst support for the methanol oxidation reaction (MOR). The structure, morphology and composition of the synthesized TiNiN/CNT-rGO exhibits a uniform particle dispersion with high purity and interpenetrating 3D network structure. Notably, Pt/TiNiN/CNT-rGO catalyst exhibits significantly improved catalytic activity and durability for methanol oxidation in comparison with Pt/CNT-rGO and conventional Pt/C (JM). The outstanding electrochemical performance was attributed to structure and properties. That is, the 3D CNT-rGO provided a fast transport network for charge-transfer and mass-transfer as well as TiNiN NPs with good synergistic effect and the strong electronic coupling between different domains in TiNiN/CNT-rGO, thus the catalytic activity of the novel catalyst is greatly improved. These results evidences 3D TiNiN/CNT-rGO as a promising catalyst support for a wide range of applications in fuel cells.

Platinum-nickel alloy nanoparticles supported on carbon for 3-pentanone hydrogenation

Energy Technology Data Exchange (ETDEWEB)

Zhu, Lihua, E-mail: lihuazhu@stu.xmu.edu.cn [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Zheng, Tuo; Yu, Changlin [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Zheng, Jinbao [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Tang, Zhenbiao [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Zhang, Nuowei [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Shu, Qing [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Chen, Bing H., E-mail: chenbh@xmu.edu.cn [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China)

2017-07-01

Highlights: • The PtNi/Ni(OH){sub 2}/C catalyst was successfully synthesized at room temperature. • PtNi alloy/C was obtained after PtNi/Ni(OH){sub 2}/C reduced in hydrogen at 300 °C. • Nanostructures of the PtNi catalysts were characterized by numerous techniques. • PtNi alloy/C exhibited high catalytic activity for 3-pentanone hydrogenation. - Abstract: In this work, we prepared the Ni/Ni(OH){sub 2}/C sample at room temperature by hydrazine hydrate reducing method. The galvanic replacement reaction method was applied to deposit platinum on the Ni/Ni(OH){sub 2} nanoparticles, to prepare the PtNi/Ni(OH){sub 2}/C catalyst. The catalyst of platinum-nickel alloy nanoparticles supported on carbon (signed as PtNi/C) was obtained by the thermal treatment of PtNi/Ni(OH){sub 2}/C in flowing hydrogen at 300 °C for 2 h. The size, nanostructure, surface properties, Pt and Ni chemical states of the PtNi/C catalyst were analyzed using powder X-ray diffraction (XRD), transmission electron microscope (TEM) and high resolution transmission electron microscope (HRTEM), high-angle annular dark-field scanning TEM (HAADF-STEM) and elemental energy dispersive X-ray spectroscopy (EDS) line scanning, X-ray photoelectron spectroscopy (XPS) and high-sensitivity low-energy ion scattering spectroscopy (HS-LEIS) techniques. The as-synthesized PtNi/C catalyst showed enhanced catalytic performance relative to the Ni/Ni(OH){sub 2}/C, Ni/C, Pt/C and PtNi/Ni(OH){sub 2}/C catalysts for 3-pentanone hydrogenation due to electron synergistic effect between Pt and Ni species in the PtNi/C catalyst. The PtNi/C catalyst also had exceling stability, with industrial application value.

Use of deuterium n. m. r. spectroscopy in mechanistic studies of exchange reactions of ethers on supported metal catalysts

Energy Technology Data Exchange (ETDEWEB)

Campbell, J.A.; Kemball, Charles; McDougall, G.S.

1987-10-01

Exchange reactions of diethyl ether (DEE) and tetrahydrofuran (THF) with deuterium have been studied over supported nickel, palladium, platinum, and rhodium catalysts. Products from most of the systems were analysed by deuterium n.m.r. spectroscopy (55.28 MHz) which gave quantitative results about the distribution of deuterium in the exchanged ethers. The results confirm earlier conclusions about the mechanism of the exchange of DEE and provide new evidence about the reactions of THF. Some hydrogenolysis occurred simultaneously with exchange of THF over both nickel and platinum.

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

Energy Technology Data Exchange (ETDEWEB)

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

2008-04-15

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

Catalytic reduction of NOx in gasoline engine exhaust over copper- and nickel-exchanged X-zeolite catalysts

International Nuclear Information System (INIS)

Bhattacharyya, S.; Das, R.K.

2001-01-01

Catalytic removal of NO x in engine exhaust gases can be accomplished by non-selective reduction, selective reduction and decomposition. Noble metals are extensively used for non-selective reduction of NO x and up to 90% of engine NO x emissions can be reduced in a stoichiometric exhaust. This requirement of having the stoichiometric fuel-air ratio acts against efficiency improvement of engines. Selective NO x reduction in the presence of different reductants such as, NH 3 , urea or hydrocarbons, requires close control of the amount of reductant being injected which otherwise may be emitted as a pollutant. Catalytic decomposition is the best option for NO x removal. Nevertheless, catalysts which are durable, economic and active for NO x reduction at normal engine exhaust temperature ranges are still being investigated. Three catalysts based on X-zeolite have been developed by exchanging the Na+ ion with copper, nickel and copper-nickel metal ions and applied to the exhaust of a stationary gasoline engine to explore their potential for catalytic reduction of NO x under a wide range of engine and exhaust conditions. Some encouraging results have been obtained. The catalyst Cu-X exhibits much better NO x reduction performance at any temperature in comparison to Cu-Ni-X and Ni-X; while Cu-Ni-X catalyst exhibits slightly better performance than Ni-X catalyst. Maximum NO x efficiency achieved with Cu-X catalyst is 59.2% at a space velocity (sv) of 31 000 h -1 ; while for Cu-Ni-X and Ni-X catalysts the equivalent numbers are 60.4% and 56% respectively at a sv of 22 000 h -1 . Unlike noble metals, the doped X-zeolite catalysts exhibit significant NO x reduction capability for a wide range of air/fuel ratio and with a slower rate of decline as well with increase in air/fuel ratio. (author)

Impeded solid state reactions and transformations in ceramic catalysts supports and catalysts

Directory of Open Access Journals (Sweden)

Ernő E. Kiss

2012-12-01

Full Text Available Impeded chemical reactions and impeded polymorphous transformation in materials are discussed, as desired effects, for stabilization of ceramic catalyst supports and ceramic based catalysts. This paper gives a short overview about the possibilities of slowing down the aging processes in ceramic catalyst supports and catalysts. Special attention is given to alumina and titania based catalysts.

Characterization of composite metal-ceramic of nickel-oxide cerium doped gadolinium

International Nuclear Information System (INIS)

Silva, M.L.A. da; Varela, M.C.R.S.

2016-01-01

Composite nickel doped cerium oxide are used in SOFC anode materials. In this study we evaluated the effect of the presence of gadolinium on the properties of composite nickel and ceria and. The supports were synthesized by sol-gel method. The impregnation with nickel nitrate was taken sequentially, followed by calcination. The materials were characterized by X-ray diffraction, measurement of specific surface area, temperature programmed reduction, Raman spectroscopy. The presence of gadolinium retained the fluorite structure of ceria by forming a solid solution, also not influencing significantly on the specific surface area of the support. On the other hand, there was a decrease in the area catalysts, which can be attributed to sintering of nickel. Furthermore, addition of gadolinium favored the formation of intrinsic and extrinsic vacancies in cerium oxide, which leads to an increase in the ionic conductivity of the solid, desirable property for an SOFC anode catalyst. (author)

Increase oil recovery of heavy oil in combustion tube using a new catalyst based nickel ionic solution

Energy Technology Data Exchange (ETDEWEB)

Ramirez-Garnica, M.A.; Hernandez-Perez, J.R.; Cabrera-Reves, M.C.; Schacht-Hernandez, P. [Inst. Mexicano del Petroleo, Mexico City (Mexico); Mamora, D.D. [Society of Petroleum Engineers, Richardson, TX (United States)]|[Texas A and M Univ., College Station, TX (United States)

2008-10-15

An ionic liquid-based nickel catalyst was used in conjunction with a combustion tube as an in situ process for heavy oil. The experimental system was comprised of a fluid injection system; a combustion tube; a fluid production system; a gas chromatograph; and a data recording system. Injected nitrogen and air was controlled by a mass flow controller. Nitrogen was used to pressurize the combustion tube and flush the system. Air was injected at a rate of 3 L per minute throughout the combustion run. Liquids leaving the combustion tube passed through a 2-stage separation process. Gases passing through the condenser were kept at low temperatures. Fractions of produced gas were analyzed by the chromatograph. Data loggers were used to obtain data at 30 second intervals. Two combustion experiments were conducted to obtain production times, temperature profiles, and the quality of the oil produced by the catalyst. Combustion tests were conducted with and without the catalyst. An analysis of the experimental data showed that use of the nickel catalyst resulted in increases in oil production as well as higher combustion efficiencies. Use of the catalyst also resulted in a faster combustion front and accelerated oil production. It was concluded that the produced oil contained fewer impurities than oil produced during the control experiment. 23 refs., 3 tabs., 9 figs.

Nickel-based xerogel catalysts: Synthesis via fast sol-gel method and application in catalytic hydrogenation of p-nitrophenol to p-aminophenol

Energy Technology Data Exchange (ETDEWEB)

Feng, Jin; Wang, Qiang; Fan, Dongliang; Ma, Lirong; Jiang, Deli; Xie, Jimin, E-mail: xiejm391@sohu.com; Zhu, Jianjun, E-mail: zhjj029@sina.com

2016-09-30

Graphical abstract: In order to investigate the roles of three-dimensional network structure and calcium on Ni catalysts, the Ni, Ni-Al{sub 2}O{sub 3}, Ni-Ca-Al{sub 2}O{sub 3} xerogel catalysts were successfully synthesized via the fast sol-gel process and chemical reduction method. - Highlights: • Epoxide-driven sol-gel and chemical reduction method subsequently were used to prepare Ni, Ni-Al{sub 2}O{sub 3} and Ni-Ca-Al{sub 2}O{sub 3} catalysts. • Three-dimensional network structure of the gel was employed to adjust the size and distribution of Ni nanoparticles. • Calcium was employed to shorten the gelation time, improve the nickel dispersion, decrease thenickel particle size and strengthen the Ni-Al{sub 2}O{sub 3} interaction. • The rate constants of Ni-Ca-Al2O3 catalysts (2.85 × 10{sup −3} s{sup −1}) is 2.8 times higher than the Ni catalysts (1.02 × 10{sup −3} s{sup −1}) and 2 times higher than the Ni-Al{sub 2}O{sub 3} catalysts(1.42 × 10{sup −3} s{sup −1}). • After 5 cycles, the conversion of PNP to PAP catalyzed by Ni, Ni-Al{sub 2}O{sub 3}, Ni-Ca-Al{sub 2}O{sub 3} remained 85%, 82%, 80%, respectively. - Abstract: In order to investigate the roles of three-dimensional network structure and calcium on Ni catalysts, the Ni, Ni-Al{sub 2}O{sub 3}, Ni-Ca-Al{sub 2}O{sub 3} xerogel catalysts were successfully synthesized via the fast sol-gel process and chemical reduction method. The crystal structure of three different catalysts was observed with X-ray powder diffraction (XRD). Transmission electron microscopy (TEM), scanning electron microscopy (SEM) and nitrogen adsorption-desorption were employed to investigate the role of network structure of xerogel catalysts and the size distribution of Ni nanoparticles. The catalyst composition was determined by inductively coupled plasma-optical emission spectrometry (ICP-OES) measurement and energy-dispersive X-ray spectroscopy (EDS). Temperature-programmed reduction (TPR) experiments were carried

Carbons and carbon supported catalysts in hydroprocessing

Energy Technology Data Exchange (ETDEWEB)

Furimsky, Edward

2009-07-01

This book is a comprehensive summary of recent research in the field and covers all areas of carbons and carbon materials. The potential application of carbon supports, particularly those of carbon black (CB) and activated carbon (AC) in hydroprocessing catalysis are covered. Novel carbon materials such as carbon fibers and carbon nano tubes (CNT) are also covered, including the more recent developments in the use of fullerenes in hydroprocessing applications. Although the primary focus of this book is on carbons and carbon supported catalysts, it also identifies the difference in the effect of carbon supports compared with the oxidic supports, particularly that of the Al{sub 2}O{sub 3}. The difference in catalyst activity and stability was estimated using both model compounds and real feeds under variable conditions. The conditions applied during the preparation of carbon supported catalysts are also comprehensively covered and include various methods of pretreatment of carbon supports to enhance catalyst performance. The model compounds results consistently show higher hydrodesulfurization and hydrodeoxygenation activities of carbon supported catalysts than that of the Al{sub 2}O{sub 3} supported catalysts. Also, the deactivation of the former catalysts by coke deposition was much less evident. Chapter 6.3.1.3 is on carbon-supported catalysts: coal-derived liquids.

Bioleaching of nickel from spent petroleum catalyst using Acidithiobacillus thiooxidans DSM- 11478.

Science.gov (United States)

Sharma, Mohita; Bisht, Varsha; Singh, Bina; Jain, Pratiksha; Mandal, Ajoy K; Lal, Banwari; Sarma, Priyangshu M

2015-06-01

The present work deals with optimization of culture conditions and process parameters for bioleaching of spent petroleum catalyst collected from a petroleum refinery. The efficacy of Ni bioleaching from spent petroleum catalyst was determined using pure culture of Acidithiobacillus thiooxidans DSM- 11478. The culture conditions of pH, temperature and headspace volume to media volume ratio were optimized. EDX analysis was done to confirm the presence of Ni in the spent catalyst after roasting it to decoke its surface. The optimum temperature for A. thiooxidans DSM-11478 growth was found to be 32 degrees C. The enhanced recovery of nickel at very low pH was attributed to the higher acidic strength of sulfuric acid produced in the culture medium by the bacterium. During the bioleaching process, 89% of the Ni present in the catalyst waste could be successfully recovered in optimized conditions. This environment friendly bioleaching process proved efficient than the chemical method. Taking leads from the lab scale results, bioleaching in larger volumes (1, 5 and 10 L) was also performed to provide guidelines for taking up this technology for in situ industrial waste management.

Low-cost removal of organic pollutants with nickel nanoparticle loaded ordered macroporous hydrogel as high performance catalyst

Energy Technology Data Exchange (ETDEWEB)

Tang, Mingyi, E-mail: tmyi@tjcu.edu.cn [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Huang, Guanbo, E-mail: gbhuang2007@hotmail.com [Department of Chemistry, School of Science, Tianjin University, Tianjin 300072 (China); Zhang, Sai [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Liu, Yue [Department of Chemistry, School of Science, Tianjin University, Tianjin 300072 (China); Li, Xianxian [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Wang, Xingrui [Department of Chemistry, School of Science, Tianjin University, Tianjin 300072 (China); Pang, Xiaobo [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Qiu, Haixia, E-mail: qhx@tju.edu.cn [Department of Chemistry, School of Science, Tianjin University, Tianjin 300072 (China)

2014-06-01

A facile route for the in situ preparation of catalytically active Ni nanoparticles (NPs) in ordered macroporous hydrogel (OMH) has been developed. The hydrogel was fabricated based on polystyrene colloid template. The electronegativity of amide and carboxyl groups on the poly(acrylamide-co-acryl acid) chains of the hydrogel caused strong binding of Ni{sup 2+} ions which made them distribute uniformly inside the hydrogel. When immersed in NaBH{sub 4} aqueous solution, the Ni{sup 2+} ions on the hydrogel were reduced to Ni NPs. The resultant Ni NPs loaded OMH showed good catalytic activity for the reduction of a common organic pollutant, 4-nitrophenol, with NaBH{sub 4}. A kinetic study of the catalytic reaction was carried out. The rate constant per unit weight could reach 0.53 s{sup −1} g{sup −1}, which is much better than many common hydrogel loaded nickel catalysts. Moreover, the current catalyst can be easily separated and recovered with stable catalytic activity. - Highlights: • A new poly(acrylamide-co-acryl acid) hydrogel with ordered macropores. • A simple in situ fabrication of nickel nanoparticles under mild conditions. • High-performance heterogeneous catalyst for removal of nitrophenol from water. • Good recyclability of catalyst without any complicated regeneration process.

Low-cost removal of organic pollutants with nickel nanoparticle loaded ordered macroporous hydrogel as high performance catalyst

International Nuclear Information System (INIS)

Tang, Mingyi; Huang, Guanbo; Zhang, Sai; Liu, Yue; Li, Xianxian; Wang, Xingrui; Pang, Xiaobo; Qiu, Haixia

2014-01-01

A facile route for the in situ preparation of catalytically active Ni nanoparticles (NPs) in ordered macroporous hydrogel (OMH) has been developed. The hydrogel was fabricated based on polystyrene colloid template. The electronegativity of amide and carboxyl groups on the poly(acrylamide-co-acryl acid) chains of the hydrogel caused strong binding of Ni 2+ ions which made them distribute uniformly inside the hydrogel. When immersed in NaBH 4 aqueous solution, the Ni 2+ ions on the hydrogel were reduced to Ni NPs. The resultant Ni NPs loaded OMH showed good catalytic activity for the reduction of a common organic pollutant, 4-nitrophenol, with NaBH 4 . A kinetic study of the catalytic reaction was carried out. The rate constant per unit weight could reach 0.53 s −1  g −1 , which is much better than many common hydrogel loaded nickel catalysts. Moreover, the current catalyst can be easily separated and recovered with stable catalytic activity. - Highlights: • A new poly(acrylamide-co-acryl acid) hydrogel with ordered macropores. • A simple in situ fabrication of nickel nanoparticles under mild conditions. • High-performance heterogeneous catalyst for removal of nitrophenol from water. • Good recyclability of catalyst without any complicated regeneration process

Study on the influence of nickel and Al{sub 2}O{sub 3} support on MoS{sub 2} as hydrodenitrogenation catalysts

Energy Technology Data Exchange (ETDEWEB)

Hein, J.; Hrabar, A.; Gutierrez, O.Y.; Lercher, J.A. [Technische Univ. Muenchen, Garching (Germany). Catalysis Research Center

2012-07-01

Alumina-supported Mo and Ni-Mo catalysts as well as an unsupported NiMo catalyst were characterized and tested in the hydrodenitrogenation (HDN) of quinoline in the presence of dibenzothiophene (DBT). The supported catalysts had a well dispersed MoS{sub 2} phase with an average stacking degree around two and slabs length below 10 nm. The unsupported NiMo sulfide catalyst exhibited long, multistacked MoS{sub 2} slabs and contained segregated Ni{sub x}S{sub y} phases. The formation of the Ni-Mo-S phase in both Ni containing catalysts was verified by X-ray absorption spectroscopy, whereas the concentration of coordinatively unsaturated sites was higher for the supported Mo and Ni-Mo catalysts than for the unsupported one. All catalysts were active in the HDN of quinoline and hydrodesulfurization of DBT. The catalytic activity increased in the order Mo/Al{sub 2}O{sub 3} < NiMo/unsupported < Ni-Mo/Al{sub 2}O{sub 3}. Thus, the influence on the catalytic activity of the promoter metal Ni is more important than the presence of a support due to the formation of the Ni-Mo-S phase (more active than MoS{sub 2}). (orig.)

Oxidation catalysts on alkaline earth supports

Science.gov (United States)

Mohajeri, Nahid

2017-03-21

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

The effect of titanium nickel nitride decorated carbon nanotubes-reduced graphene oxide hybrid support for methanol oxidation

Energy Technology Data Exchange (ETDEWEB)

Liu, Gen [School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou, Guangdong 510006 (China); Pan, Zhanchang, E-mail: panzhanchang@163.com [School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou, Guangdong 510006 (China); Li, Wuyi; Yu, Ke [School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou, Guangdong 510006 (China); Xia, Guowei; Zhao, Qixiang; Shi, Shikun [Victory Giant Technology (Hui Zhou) Co., Ltd., Huizhou 516083 (China); Hu, Guanghui; Xiao, Chumin; Wei, Zhigang [School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou, Guangdong 510006 (China)

2017-07-15

Highlights: • TiNiN/CNT-rGO support with an interactive three-dimensional structure and high surface area was synthesized. • Pt nanoparticles with small size were well dispersed on TiNiN/CNT-rGO support. • Pt/TiNiN/CNT-rGO shows remarkably enhanced methanol oxidation activity and durability. - Abstract: Titanium nickel nitride (TiNiN) decorated three-dimensional (3D) carbon nanotubes-reduced graphene oxide (CNT-rGO), a fancy 3D platinum (Pt)-based catalyst hybrid support, is prepared by a solvothermal process followed by a nitriding process, which is tested as anodic catalyst support for the methanol oxidation reaction (MOR). The structure, morphology and composition of the synthesized TiNiN/CNT-rGO exhibits a uniform particle dispersion with high purity and interpenetrating 3D network structure. Notably, Pt/TiNiN/CNT-rGO catalyst exhibits significantly improved catalytic activity and durability for methanol oxidation in comparison with Pt/CNT-rGO and conventional Pt/C (JM). The outstanding electrochemical performance was attributed to structure and properties. That is, the 3D CNT-rGO provided a fast transport network for charge-transfer and mass-transfer as well as TiNiN NPs with good synergistic effect and the strong electronic coupling between different domains in TiNiN/CNT-rGO, thus the catalytic activity of the novel catalyst is greatly improved. These results evidences 3D TiNiN/CNT-rGO as a promising catalyst support for a wide range of applications in fuel cells.

The effect of titanium nickel nitride decorated carbon nanotubes-reduced graphene oxide hybrid support for methanol oxidation

International Nuclear Information System (INIS)

Liu, Gen; Pan, Zhanchang; Li, Wuyi; Yu, Ke; Xia, Guowei; Zhao, Qixiang; Shi, Shikun; Hu, Guanghui; Xiao, Chumin; Wei, Zhigang

2017-01-01

Highlights: • TiNiN/CNT-rGO support with an interactive three-dimensional structure and high surface area was synthesized. • Pt nanoparticles with small size were well dispersed on TiNiN/CNT-rGO support. • Pt/TiNiN/CNT-rGO shows remarkably enhanced methanol oxidation activity and durability. - Abstract: Titanium nickel nitride (TiNiN) decorated three-dimensional (3D) carbon nanotubes-reduced graphene oxide (CNT-rGO), a fancy 3D platinum (Pt)-based catalyst hybrid support, is prepared by a solvothermal process followed by a nitriding process, which is tested as anodic catalyst support for the methanol oxidation reaction (MOR). The structure, morphology and composition of the synthesized TiNiN/CNT-rGO exhibits a uniform particle dispersion with high purity and interpenetrating 3D network structure. Notably, Pt/TiNiN/CNT-rGO catalyst exhibits significantly improved catalytic activity and durability for methanol oxidation in comparison with Pt/CNT-rGO and conventional Pt/C (JM). The outstanding electrochemical performance was attributed to structure and properties. That is, the 3D CNT-rGO provided a fast transport network for charge-transfer and mass-transfer as well as TiNiN NPs with good synergistic effect and the strong electronic coupling between different domains in TiNiN/CNT-rGO, thus the catalytic activity of the novel catalyst is greatly improved. These results evidences 3D TiNiN/CNT-rGO as a promising catalyst support for a wide range of applications in fuel cells.

The use of deuterium n.m.r. spectroscopy in mechanistic studies of exchange reactions of ethers on supported metal catalysts

International Nuclear Information System (INIS)

Campbell, J.A.; Kemball, Charles; McDougall, G.S.

1987-01-01

Exchange reactions of diethyl ether (DEE) and tetrahydrofuran (THF) with deuterium have been studied over supported nickel, palladium, platinum, and rhodium catalysts. Products from most of the systems were analysed by deuterium n.m.r. spectroscopy (55.28 MHz) which gave quantitative results about the distribution of deuterium in the exchanged ethers. The results confirm earlier conclusions about the mechanism of the exchange of DEE and provide new evidence about the reactions of THF. Some hydrogenolysis occurred simultaneously with exchange of THF over both nickel and platinum. (author)

Hydrothermal performance of catalyst supports

Energy Technology Data Exchange (ETDEWEB)

Elam, Jeffrey W.; Marshall, Christopher L.; Libera, Joseph A.; Dumesic, James A.; Pagan-Torres, Yomaira J.

2018-04-10

A high surface area catalyst with a mesoporous support structure and a thin conformal coating over the surface of the support structure. The high surface area catalyst support is adapted for carrying out a reaction in a reaction environment where the thin conformal coating protects the support structure within the reaction environment. In various embodiments, the support structure is a mesoporous silica catalytic support and the thin conformal coating comprises a layer of metal oxide resistant to the reaction environment which may be a hydrothermal environment.

A comparative study of alumina-supported Ni catalysts prepared by photodeposition and impregnation methods on the catalytic ozonation of 2,4-dichlorophenoxyacetic acid

International Nuclear Information System (INIS)

Rodríguez, Julia L.; Valenzuela, Miguel A.; Tiznado, Hugo; Poznyak, Tatiana; Chairez, Isaac; Magallanes, Diana

2017-01-01

The heterogeneous catalytic ozonation on unsupported and supported oxides has been successfully tested for the removal of several refractory compounds in aqueous solution. In this work, alumina-supported nickel catalysts prepared by photodeposition and impregnation methods were compared in the catalytic ozonation of 2,4-dichlorophenoxyacetic acid (2,4-D). The catalysts were characterized by high-resolution electron microscopy and X-ray photoelectron spectroscopy. The photochemical decomposition of Ni acetylacetonate to produce Ni(OH) 2 , NiO, and traces of Ni° deposited on alumina was achieved in the presence of benzophenone as a sensitizer. A similar surface composition was found with the impregnated catalyst after its reduction with hydrogen at 500 °C and exposed to ambient air. Results indicated a higher initial activity and maleic acid (byproduct) concentration with the photodeposited catalyst (1 wt% Ni) compared to the impregnated catalyst (3 wt% Ni). These findings suggest the use of the photodeposition method as a simple and reliable procedure for the preparation of supported metal oxide/metal catalysts under mild operating conditions.

A comparative study of alumina-supported Ni catalysts prepared by photodeposition and impregnation methods on the catalytic ozonation of 2,4-dichlorophenoxyacetic acid

Energy Technology Data Exchange (ETDEWEB)

Rodríguez, Julia L., E-mail: ozliliana@yahoo.com.mx [Lab. Ing. Química Ambiental. ESIQIE–Instituto Politécnico Nacional (Mexico); Valenzuela, Miguel A. [Lab.Catálisis y Materiales. ESIQIE–Instituto Politécnico Nacional. Zacatenco (Mexico); Tiznado, Hugo [Centro de Nanociencias y Nanotecnología. CNyN Universidad Nacional Autónoma de México (Mexico); Poznyak, Tatiana [Lab. Ing. Química Ambiental. ESIQIE–Instituto Politécnico Nacional (Mexico); Chairez, Isaac [Departamento de Bioprocesos, UPIBI- Instituto Politécnico Nacional (Mexico); Magallanes, Diana [Lab. Ing. Química Ambiental. ESIQIE–Instituto Politécnico Nacional (Mexico)

2017-02-15

The heterogeneous catalytic ozonation on unsupported and supported oxides has been successfully tested for the removal of several refractory compounds in aqueous solution. In this work, alumina-supported nickel catalysts prepared by photodeposition and impregnation methods were compared in the catalytic ozonation of 2,4-dichlorophenoxyacetic acid (2,4-D). The catalysts were characterized by high-resolution electron microscopy and X-ray photoelectron spectroscopy. The photochemical decomposition of Ni acetylacetonate to produce Ni(OH){sub 2}, NiO, and traces of Ni° deposited on alumina was achieved in the presence of benzophenone as a sensitizer. A similar surface composition was found with the impregnated catalyst after its reduction with hydrogen at 500 °C and exposed to ambient air. Results indicated a higher initial activity and maleic acid (byproduct) concentration with the photodeposited catalyst (1 wt% Ni) compared to the impregnated catalyst (3 wt% Ni). These findings suggest the use of the photodeposition method as a simple and reliable procedure for the preparation of supported metal oxide/metal catalysts under mild operating conditions.

Magnetic nickel ferrite nanoparticles as highly durable catalysts for catalytic transfer hydrogenation of bio-based aldehydes

DEFF Research Database (Denmark)

He, Jian; Yang, Song; Riisager, Anders

2018-01-01

Magnetic nickel ferrite (NiFe2O4) nanoparticles were exploited as stable and easily separable heterogeneous catalysts for catalytic transfer hydrogenation (CTH) of furfural to furfuryl alcohol with 2-propanol as both the hydrogen source and the solvent providing 94% product yield at 180 degrees C...

Carbon-Nanotube-Supported Bio-Inspired Nickel Catalyst and Its Integration in Hybrid Hydrogen/Air Fuel Cells.

Science.gov (United States)

Gentil, Solène; Lalaoui, Noémie; Dutta, Arnab; Nedellec, Yannig; Cosnier, Serge; Shaw, Wendy J; Artero, Vincent; Le Goff, Alan

2017-02-06

A biomimetic nickel bis-diphosphine complex incorporating the amino acid arginine in the outer coordination sphere was immobilized on modified carbon nanotubes (CNTs) through electrostatic interactions. The functionalized redox nanomaterial exhibits reversible electrocatalytic activity for the H 2 /2 H + interconversion from pH 0 to 9, with catalytic preference for H 2 oxidation at all pH values. The high activity of the complex over a wide pH range allows us to integrate this bio-inspired nanomaterial either in an enzymatic fuel cell together with a multicopper oxidase at the cathode, or in a proton exchange membrane fuel cell (PEMFC) using Pt/C at the cathode. The Ni-based PEMFC reaches 14 mW cm -2 , only six-times-less as compared to full-Pt conventional PEMFC. The Pt-free enzyme-based fuel cell delivers ≈2 mW cm -2 , a new efficiency record for a hydrogen biofuel cell with base metal catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Energy Technology Data Exchange (ETDEWEB)

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

2007-05-15

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

Urine nickel concentrations in nickel-exposed workers.

Science.gov (United States)

Bernacki, E J; Parsons, G E; Roy, B R; Mikac-Devic, M; Kennedy, C D; Sunderman, F W

1978-01-01

Electrothermal atomic absorption spectrometry was employed for analyses of nickel concentrations in urine samples from nickel-exposed workers in 10 occupational groups and from non-exposed workers in two control groups. Mean concentrations of nickel in urine were greatest in workers who were exposed to inhalation of aerosols of soluble nickel salts (e.g., workers in nickel plating operations and in an electrolytic nickel refinery). Less marked increases in urine nickel concentrations were found in groups of metal sprayers, nickel battery workers, bench mechanics and are welders. No significant increases in mean concentrations of nickel were found in urine samples from workers who performed grinding, buffing and polishing of nickel-containing alloys or workers in a coal gasification plant who employed Raney nickel as a hydrogenation catalyst. Measurements of nickel concentrations in urine are more sensitive and practical than measurements of serum nickel concentrations for evaluation of nickel exposures in industrial workers.

Catalytic Pyrolysis of Tar Model Compound with Various Bio-Char Catalysts to Recycle Char from Biomass Pyrolysis

Directory of Open Access Journals (Sweden)

Jinmiao Liu

2016-03-01

Full Text Available Tar and char can be regarded as unwanted byproducts during the gasification process. In this study, three types of catalyst, i.e., biomass char (bio-char, nickel supported on biomass (Ni+bio-char, and nickel supported on bio-char (bio-char+Ni, were studied to compare the catalytic effects of different preparation methods on tar model compound removal. The structural characteristics of the three catalysts were also investigated by X-ray diffraction (XRD, scanning electron microscopy (SEM, and Brunauer-Emmett-Teller (BET methods. The results revealed that Ni+bio-char catalyst showed much higher activity for the reformation of toluene (C7H8 as a tar model compound than the other two catalysts. Toluene could be completely converted to small gas molecules at a conversion rate of 99.92% at 800 °C, and the maximum yield of gas was 432 mL/(mL C7H8. In particular, the H2 and CH4 yields were 339 and 85 mL/(mL C7H8 at 850 °C, respectively. An N2 absorption-desorption experiment demonstrated that the specific surface area of Ni+bio-char was 32.87 times that of bio-char and 8.39 times that of bio-char+Ni. Moreover, metallic nickel (Ni0 particles could be generated in the carbon matrix of Ni+bio-char catalyst. SEM analysis confirmed that the Ni+bio-char catalyst had a more porous structure. Nickel supported on biomass might be a promising catalyst for tar reformation because of its excellent catalytic activities.

In-situ hydrodeoxygenation of phenol by supported Ni catalyst-explanation for catalyst performance

DEFF Research Database (Denmark)

Wang, Ze; Zeng, Ying; Lin, Weigang

2017-01-01

In-situ hydrodeoxygenation of phenol with aqueous hydrogen donor over supported Ni catalyst was investigated. The supported Ni catalysts exerted very poor performance, if formic acid was used as the hydrogen donor. Catalyst modification by loading K, Na, Mg or La salt could not make the catalyst...... performance improved. If gaseous hydrogen was used as the hydrogen source the activity of Ni/Al2O3 was pretty high. CO2 was found poisonous to the catalysis, due to the competitive adoption of phenol with CO2. If formic acid was replaced by methanol, the catalyst performance improved remarkably, with major...... products of cyclohexanone and cyclohexanol. The better effect of methanol enlightened the application of the supported Ni catalyst in in-situ hydrodeoxygenation of phenol....

Nickel-based anodic electrocatalysts for fuel cells and water splitting

Science.gov (United States)

Chen, Dayi

Our world is facing an energy crisis, so people are trying to harvest and utilize energy more efficiently. One of the promising ways to harvest energy is via solar water splitting to convert solar energy to chemical energy stored in hydrogen. Another of the options to utilize energy more efficiently is to use fuel cells as power sources instead of combustion engines. Catalysts are needed to reduce the energy barriers of the reactions happening at the electrode surfaces of the water-splitting cells and fuel cells. Nickel-based catalysts happen to be important nonprecious electrocatalysts for both of the anodic reactions in alkaline media. In alcohol fuel cells, nickel-based catalysts catalyze alcohol oxidation. In water splitting cells, they catalyze water oxidation, i.e., oxygen evolution. The two reactions occur in a similar potential range when catalyzed by nickel-based catalysts. Higher output current density, lower oxidation potential, and complete substrate oxidation are preferred for the anode in the applications. In this dissertation, the catalytic properties of nickel-based electrocatalysts in alkaline medium for fuel oxidation and oxygen evolution are explored. By changing the nickel precursor solubility, nickel complex nanoparticles with tunable sizes on electrode surfaces were synthesized. Higher methanol oxidation current density is achieved with smaller nickel complex nanoparticles. DNA aggregates were used as a polymer scaffold to load nickel ion centers and thus can oxidize methanol completely at a potential about 0.1 V lower than simple nickel electrodes, and the methanol oxidation pathway is changed. Nickel-based catalysts also have electrocatalytic activity towards a wide range of substrates. Experiments show that methanol, ethanol, glycerol and glucose can be deeply oxidized and carbon-carbon bonds can be broken during the oxidation. However, when comparing methanol oxidation reaction to oxygen evolution reaction catalyzed by current nickel

Adsorption of heavy metal ion from aqueous solution by nickel oxide nano catalyst prepared by different methods

Directory of Open Access Journals (Sweden)

Amira M. Mahmoud

2015-03-01

Full Text Available Environmental pollution by heavy metal is arising as the most endangering tasks to both water sources and atmosphere quality today. The treatment of heavy metals is of special concern due to their recalcitrance and persistence in the environment. To limit the spread of the heavy metals within water sources, nickel oxide nanoparticles adsorbents were synthesized and characterized with the aim of removal of one of the aggressive heavy elements, namely; lead ions. Nano nickel oxide adsorbents were prepared using NaOH and oxalic acid dissolved in ethanol as precursors. The results indicated that adsorption capacity of Pb(II ion by NiO-org catalyst is favored than that prepared using NaOH as a precipitant. Nickel oxide nanoparticles prepared by the two methods were characterized structurally and chemically through XRD, DTA, TGA, BET and FT-IR. Affinity and efficiency sorption parameters of the solid nano NiO particles, such as; contact time, initial concentration of lead ions and the dosage of NiO nano catalyst and competitive adsorption behaviors were studied. The results showed that the first-order reaction law fit the reduction of lead ion, also showed good linear relationship with a correlation coefficient (R2 larger than 0.9.

Supported catalyst systems and method of making biodiesel products using such catalysts

Science.gov (United States)

Kim, Manhoe; Yan, Shuli; Salley, Steven O.; Ng, K. Y. Simon

2015-10-20

A heterogeneous catalyst system, a method of preparing the catalyst system and a method of forming a biodiesel product via transesterification reactions using the catalyst system is disclosed. The catalyst system according to one aspect of the present disclosure represents a class of supported mixed metal oxides that include at least calcium oxide and another metal oxide deposited on a lanthanum oxide or cerium oxide support. Preferably, the catalysts include CaO--CeO.sub.2ZLa.sub.2O.sub.3 or CaO--La.sub.2O.sub.3/CeO.sub.2. Optionally, the catalyst may further include additional metal oxides, such as CaO--La.sub.2O.sub.3--GdOxZLa.sub.2O.sub.3.

Co-Assembled Supported Catalysts: Synthesis of Nano-Structured Supported Catalysts with Hierarchic Pores through Combined Flow and Radiation Induced Co-Assembled Nano-Reactors

Directory of Open Access Journals (Sweden)

Galip Akay

2016-05-01

Full Text Available A novel generic method of silica supported catalyst system generation from a fluid state is presented. The technique is based on the combined flow and radiation (such as microwave, thermal or UV induced co-assembly of the support and catalyst precursors forming nano-reactors, followed by catalyst precursor decomposition. The transformation from the precursor to supported catalyst oxide state can be controlled from a few seconds to several minutes. The resulting nano-structured micro-porous silica supported catalyst system has a surface area approaching 300 m2/g and X-ray Diffraction (XRD-based catalyst size controlled in the range of 1–10 nm in which the catalyst structure appears as lamellar sheets sandwiched between the catalyst support. These catalyst characteristics are dependent primarily on the processing history as well as the catalyst (Fe, Co and Ni studied when the catalyst/support molar ratio is typically 0.1–2. In addition, Ca, Mn and Cu were used as co-catalysts with Fe and Co in the evaluation of the mechanism of catalyst generation. Based on extensive XRD, Scanning Electron Microscopy (SEM and Transmission Electron Microscopy (TEM studies, the micro- and nano-structure of the catalyst system were evaluated. It was found that the catalyst and silica support form extensive 0.6–2 nm thick lamellar sheets of 10–100 nm planar dimensions. In these lamellae, the alternate silica support and catalyst layer appear in the form of a bar-code structure. When these lamellae structures pack, they form the walls of a micro-porous catalyst system which typically has a density of 0.2 g/cm3. A tentative mechanism of catalyst nano-structure formation is provided based on the rheology and fluid mechanics of the catalyst/support precursor fluid as well as co-assembly nano-reactor formation during processing. In order to achieve these structures and characteristics, catalyst support must be in the form of silane coated silica nano

Attrition resistant Fischer-Tropsch catalyst and support

Science.gov (United States)

Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

2004-05-25

A catalyst support having improved attrition resistance and a catalyst produced therefrom. The catalyst support is produced by a method comprising the step of treating calcined .gamma.-alumina having no catalytic material added thereto with an acidic aqueous solution having an acidity level effective for increasing the attrition resistance of the calcined .gamma.-alumina.

Catalytic reduction of NO{sub x} in gasoline engine exhaust over copper- and nickel-exchanged X-zeolite catalysts

Energy Technology Data Exchange (ETDEWEB)

Bhattacharyya, S. [Indian Inst. of Technology, Kharagpur (India). Dept. of Mechanical Engineering; Das, R.K. [Indian School of Mines, Dhanbad (India). Dept. of Engineering and Mining Machinery

2001-10-11

Catalytic removal of NO{sub x} in engine exhaust gases can be accomplished by non-selective reduction, selective reduction and decomposition. Noble metals are extensively used for non-selective reduction of NO{sub x} and up to 90% of engine NO{sub x} emissions can be reduced in a stoichiometric exhaust. This requirement of having the stoichiometric fuel-air ratio acts against efficiency improvement of engines. Selective NO{sub x} reduction in the presence of different reductants such as, NH{sub 3}, urea or hydrocarbons, requires close control of the amount of reductant being injected which otherwise may be emitted as a pollutant. Catalytic decomposition is the best option for NO{sub x} removal. Nevertheless, catalysts which are durable, economic and active for NO{sub x} reduction at normal engine exhaust temperature ranges are still being investigated. Three catalysts based on X-zeolite have been developed by exchanging the Na+ ion with copper, nickel and copper-nickel metal ions and applied to the exhaust of a stationary gasoline engine to explore their potential for catalytic reduction of NO{sub x} under a wide range of engine and exhaust conditions. Some encouraging results have been obtained. The catalyst Cu-X exhibits much better NO{sub x} reduction performance at any temperature in comparison to Cu-Ni-X and Ni-X; while Cu-Ni-X catalyst exhibits slightly better performance than Ni-X catalyst. Maximum NO{sub x} efficiency achieved with Cu-X catalyst is 59.2% at a space velocity (sv) of 31 000 h{sup -1}; while for Cu-Ni-X and Ni-X catalysts the equivalent numbers are 60.4% and 56% respectively at a sv of 22 000 h{sup -1}. Unlike noble metals, the doped X-zeolite catalysts exhibit significant NO{sub x} reduction capability for a wide range of air/fuel ratio and with a slower rate of decline as well with increase in air/fuel ratio. (author)

The effect of noble metals on catalytic methanation reaction over supported Mn/Ni oxide based catalysts

Directory of Open Access Journals (Sweden)

Wan Azelee Wan Abu Bakar

2015-09-01

Full Text Available Carbon dioxide (CO2 in sour natural gas can be removed using green technology via catalytic methanation reaction by converting CO2 to methane (CH4 gas. Using waste to wealth concept, production of CH4 would increase as well as creating environmental friendly approach for the purification of natural gas. In this research, a series of alumina supported manganese–nickel oxide based catalysts doped with noble metals such as ruthenium and palladium were prepared by wetness impregnation method. The prepared catalysts were run catalytic screening process using in-house built micro reactor coupled with Fourier Transform Infra Red (FTIR spectroscopy to study the percentage CO2 conversion and CH4 formation analyzed by GC. Ru/Mn/Ni(5:35:60/Al2O3 calcined at 1000 °C was found to be the potential catalyst which gave 99.74% of CO2 conversion and 72.36% of CH4 formation at 400 °C reaction temperature. XRD diffractogram illustrated that the supported catalyst was in polycrystalline with some amorphous state at 1000 °C calcination temperature with the presence of NiO as active site. According to FESEM micrographs, both fresh and used catalysts displayed spherical shape with small particle sizes in agglomerated and aggregated mixture. Nitrogen Adsorption analysis revealed that both catalysts were in mesoporous structures with BET surface area in the range of 46–60 m2/g. All the impurities have been removed at 1000 °C calcination temperature as presented by FTIR, TGA–DTA and EDX data.

Titanium Dioxide as a Catalyst Support in Heterogeneous Catalysis

Science.gov (United States)

Bagheri, Samira; Muhd Julkapli, Nurhidayatullaili; Bee Abd Hamid, Sharifah

2014-01-01

The lack of stability is a challenge for most heterogeneous catalysts. During operations, the agglomeration of particles may block the active sites of the catalyst, which is believed to contribute to its instability. Recently, titanium oxide (TiO2) was introduced as an alternative support material for heterogeneous catalyst due to the effect of its high surface area stabilizing the catalysts in its mesoporous structure. TiO2 supported metal catalysts have attracted interest due to TiO2 nanoparticles high activity for various reduction and oxidation reactions at low pressures and temperatures. Furthermore, TiO2 was found to be a good metal oxide catalyst support due to the strong metal support interaction, chemical stability, and acid-base property. The aforementioned properties make heterogeneous TiO2 supported catalysts show a high potential in photocatalyst-related applications, electrodes for wet solar cells, synthesis of fine chemicals, and others. This review focuses on TiO2 as a support material for heterogeneous catalysts and its potential applications. PMID:25383380

Nickel and cobalt bimetallic hydroxide catalysts for urea electro-oxidation

International Nuclear Information System (INIS)

Yan Wei; Wang Dan; Botte, Gerardine G.

2012-01-01

Nickel–Cobalt bimetallic hydroxide electrocatalysts, synthesized through a one-step electrodeposition method, were evaluated for the oxidation of urea in alkaline conditions with the intention of reducing the oxidation overpotential for this reaction. The Nickel–Cobalt bimetallic hydroxide catalysts were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS), Raman spectroscopy, cyclic voltammetry (CV), and polarization techniques. A significant reduction in the overpotential (150 mV) of the reaction was observed with the Nickel–Cobalt bimetallic hydroxide electrode (ca. 43% Co content) when compared to a nickel hydroxide electrode. The decrease of the urea oxidation potential on the Nickel–Cobalt bimetallic hydroxide electrodes reveals great potential for future applications of urea electro-oxidation, including wastewater remediation, hydrogen production, sensors, and fuel cells.

A possible highly active supported Ni dimer catalyst for O{sub 2} dissociation: A first-principles study

Energy Technology Data Exchange (ETDEWEB)

Dong, Shan [College of Physics and Materials Science, Henan Normal University, Xinxiang, Henan 453007 (China); Zhang, Yanxing, E-mail: 2016025@htu.edu.cn [College of Physics and Materials Science, Henan Normal University, Xinxiang, Henan 453007 (China); Zhang, Xilin; Mao, Jianjun [College of Physics and Materials Science, Henan Normal University, Xinxiang, Henan 453007 (China); Yang, Zongxian, E-mail: yzx@henannu.edu.cn [College of Physics and Materials Science, Henan Normal University, Xinxiang, Henan 453007 (China); Collaborative Innovation Center of Nano Functional Materials and Applications, Henan Province (China)

2017-04-30

Graphical abstract: The minimum energy paths (MEPs) for the dissociation process of O{sub 2} on the surfaces of bare YSZ (111) and Ni{sub n}/YSZ (111) (n = 1, 2 and 3). - Highlights: • The catalytic activity of supported metal catalysts is closely related to the size of metal particles. • The dissociation of O{sub 2} on the YSZ (111) surface is largely enhanced by the supported Ni cluster. • The supported Ni dimer is predicted to be the smallest Ni cluster needed for efficient O{sub 2} dissociation. • The results would provide an important reference to improve the activity and efficiency of the Ni/YSZ(111) nanocomposite catalysts in cost-effective materials. - Abstract: The adsorption and dissociation of O{sub 2} on the supported small nickel clusters with one-, two-, three-Ni atoms on yttria-stabilized zirconia (YSZ) (111) surfaces, as well as those on the bare YSZ(111) and Ni(111) surfaces are comparatively studied using ab initio density functional theory calculations. It is found that the dissociation of O{sub 2} on the YSZ(111) surface is largely enhanced by the supported Ni dimer, which is predicted to be the smallest Ni cluster needed for efficient O{sub 2} dissociation. The results would provide an important reference to improve the activity and efficiency of the Ni/YSZ(111) nanocomposite catalysts in cost-effective materials.

The effect of catalyst support on the RWGS reaction

International Nuclear Information System (INIS)

Laosiripojana, N.; Sutthisripok, W.

2004-01-01

'Full text:' Methane steam reforming is generally applied in order to produce synthesis gas mainly consist of hydrogen and carbon monoxide for later utilization in SOFC. This reaction is always carried out with the water gas shift reaction over a catalyst at elevated temperatures resulting in some carbon dioxide production. The CO/CO2 production selectivity strongly depends on the influence of water gas shift reaction. It was observed that the reactivity of this reaction depended on the type of support material. Stabilities, activities, and kinetics of the reverse water gas shift reaction (RWGS) for commercial nickel on CeO2, ZrO2, CeO2-ZrO2, TiO2, MgO, and Al2O3 supports were studied in order to observe the influence of the support on this reaction. According to the experiment, the activities of Ni/CeO2 toward the reverse water gas shift reaction (RWGS) were very high, and reached equilibrium level at approximately 600 o C (where the conversion of CO2 was closed to 1). Other oxide supports provided lower activities toward this reaction. It was observed that the activity of Ni/Al2O3 toward this reaction was the lowest. The kinetics of this reaction was also studied. Carbon dioxide presented positive effect on the reverse water gas shift reaction. The reaction orders in carbon dioxide were observed to be positive partial value between 0-1. It slightly decreased with increasing temperature for Ni/ CeO2 and Ni/CeO2-ZrO2, whereas it seemed to be independent of the operating temperature for other materials in the range of conditions studied. Hydrogen also showed positive effect on the reverse water gas shift reaction for all materials. The reaction order in hydrogen for all materials was observed to be the positive value and less than one for the range of conditions studied. The approximate values for all catalysts were between 0.45-0.65, and seemed to be independent of the operating temperature. The estimated values of the apparent activation energy for RWGS reaction

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.

Discovery of technical methanation catalysts based on computational screening

DEFF Research Database (Denmark)

Sehested, Jens; Larsen, Kasper Emil; Kustov, Arkadii

2007-01-01

Methanation is a classical reaction in heterogeneous catalysis and significant effort has been put into improving the industrially preferred nickel-based catalysts. Recently, a computational screening study showed that nickel-iron alloys should be more active than the pure nickel catalyst and at ...

Effects of P/Ni ratio and Ni content on performance of γ-Al_2O_3-supported nickel phosphides for deoxygenation of methyl laurate to hydrocarbons

International Nuclear Information System (INIS)

Zhang, Zhena; Tang, Mingxiao; Chen, Jixiang

2016-01-01

Graphical abstract: - Highlights: • The formation of AlPO_4 was unfavorable for that of nickel phosphides. • The phase compositions of nickel phosphide depended on the amount of reduced P. • Catalytic activity was determined by surface Ni site density and catalyst acidity. • HDO pathway was promoted by increasing P/Ni ratio and Ni content. • Nickel phosphide gave much higher carbon yield and lower H_2 consumption than Ni. - Abstract: γ-Al_2O_3-supported nickel phosphides (mNi-Pn) were prepared by the TPR method and tested for the deoxygenation of methyl laurate to hydrocarbons. The effects of the P/Ni ratio (n = 1.0–2.5) and Ni content (m = 5–15 wt.%) in the precursors on their structure and performance were investigated. Ni/γ-Al_2O_3 was also studied for comparison. It was found that the formation of AlPO_4 in the precursor inhibited the reduction of phosphate and so the formation of nickel phosphides. With increasing the P/Ni ratio and Ni content, the Ni, Ni_3P, Ni_1_2P_5 and Ni_2P phases orderly formed, accompanying with the increases of their particle size and the amount of weak acid sites (mainly due to P-OH group), while the CO uptake and the amount of medium strong acid sites (mainly related to Ni sites) reached maximum on 10%Ni-P1.5. In the deoxygenation reaction, compared with Ni/γ-Al_2O_3, the mNi-Pn catalysts showed much lower activities for decarbonylation, C−C hydrogenolysis and methanation due to the ligand and ensemble effects of P. The conversion and the selectivity to n-C11 and n-C12 hydrocarbons achieved maximum on 10%Ni-P 2.0 for the 10%Ni-Pn catalysts and on 8%Ni-P2.0 for the mNi-P2.0 catalysts, while the turnover frequency (TOF) of methyl laurate mainly increased with the P/Ni ratio and Ni content. We propose that TOF was influenced by the nickel phosphide phases, the catalyst acidity and the particle size as well as the synergetic effect between the Ni site and acid site. Again, the hydrodeoxygenation pathway of methyl

Catalytic pyrolysis of Tetraselmis and Isochrysis microalgae by nickel ceria based catalysts for hydrocarbon production

International Nuclear Information System (INIS)

Aysu, Tevfik; Abd Rahman, Nur Adilah; Sanna, Aimaro

2016-01-01

The catalytic pyrolysis of Tetraselmis sp. and Isochrysis sp. was carried out over ceria based catalysts in a fixed bed reactor. There was a clear effect of the catalysts on the product yields and quality, with the catalysts able to recover a large fraction of the starting microalgae energy (67–77%) in the bio-oils. Bio-oil yield was found to be higher in presence of Ni–Ce/Al_2O_3 and Ni–Ce/ZrO_2 (26 wt.%). The produced bio-oils had HHVs (higher heating values) of 34–35 MJ/kg and suffered strong deoxygenation, with O level decreased from 40–41% in the starting microalgae to 9–15%. Also, 15–20% N removal was obtained using the ceria based catalysts. The oxygen contents in the bio-oils were remarkably lower than those previously obtained using ZSM-5 (25%) and other species without catalyst (17–24%). "1H NMR and GC–MS analysis showed that the bio-oils were enriched in aliphatics and depleted in N-compounds and water using the ceria based catalysts. - Highlights: • Nickel-ceria based catalysts were evaluated for the in-situ conversion of Tetraselmis and Isochrysis microalgae. • Catalysts recovered 72–77% of the starting microalgae energy in bio-oils. • Bio-oils suffered strong deoxygenation, with O level decreased from 40–41% in the starting microalgae to 9–15%. • Bio-oils were enriched in aliphatics and depleted in N-compounds.

Thermal decomposition of supported lithium nitrate catalysts

Energy Technology Data Exchange (ETDEWEB)

Ruiz, Maria Lucia [INTEQUI (CONICET-UNSL), 25 de Mayo 384, V. Mercedes, 5730, San Luis (Argentina); Lick, Ileana Daniela [CINDECA (CONICET-UNLP), Calle 47 No 257, La Plata, 1900, Buenos Aires (Argentina); Ponzi, Marta Isabel [INTEQUI (CONICET-UNSL), 25 de Mayo 384, V. Mercedes, 5730, San Luis (Argentina); Castellon, Enrique Rodriguez; Jimenez-Lopez, Antonio [Departamento de Quimica Inorganica, Cristalografia y Mineralogia. Facultad de Ciencias, Universidad de Malaga, Campus de Teatinos, 29071 Malaga (Spain); Ponzi, Esther Natalia, E-mail: eponzi@quimica.unlp.edu.ar [CINDECA (CONICET-UNLP), Calle 47 No 257, La Plata, 1900, Buenos Aires (Argentina)

2010-02-20

New catalysts for soot combustion were prepared by impregnation of different supports (SiO{sub 2}, ZrO{sub 2} and ZrO{sub 2}.nH{sub 2}O) with a LiNO{sub 3} solution and then characterized by means of FTIR, XPS, TGA and UV-vis spectroscopy, whereby the presence of lithium nitrate in the prepared catalysts was identified and quantified. The soot combustion rate using this series of catalysts (LiNO{sub 3}/support) was compared with the activity of a series of impregnated catalysts prepared using LiOH (Li{sub 2}O/supports). Catalysts prepared using LiNO{sub 3} are found to be more active than those prepared using LiOH. The catalytic performance was also studied with a NO/O{sub 2} mixture in the feed, demonstrating that NO increases the combustion rate of soot, probably as a consequence of lithium oxide forming an 'in situ' nitrate ion.

Efficient photo-catalytic degradation of malachite green using nickel tungstate material as photo-catalyst.

Science.gov (United States)

Helaïli, N; Boudjamaa, A; Kebir, M; Bachari, K

2017-03-01

The present study focused on the evaluation of photo-catalytic and photo-electrochemical properties of the photo-catalyst based on nickel tungstate material prepared by a nitrate method through the degradation of malachite green (MG) dye's. The effect of catalyst loading and dye concentration was examined. Physico-chemical, optical, electrical, electrochemical, and photo-electrochemical properties of the prepared material were analyzed by X-ray diffraction (XRD), fourier transform-infrared spectroscopy (FTIR), BET analysis, optical reflectance diffuse (DR), scanning electron microscopy (SEM/EDX), electrical conductivity, cyclic voltammetry (CV), current intensity, mott-shottky, and nyquist. XRD revealed the formation of monoclinic structure with a small particle size. BET surface area of the sample was around 10 m 2 /g. The results show that the degradation of MG was more than 80%, achieved after 3 h of irradiation at pH 4.6 and with a catalyst loading of 75 mg. Also, it was found that the dye photo-degradation obeyed the pseudo-first order kinetic via Langmuir Hinshelwood model.

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

Deactivation of nickel catalysts in the methanization of hydrogen/carbon monoxide mixtures under pressure

Energy Technology Data Exchange (ETDEWEB)

Zeeb, H P

1979-01-01

The deactivation course of nickel methanization catalysts was investigated in the temperature range of 310/sup 0/C to 370/sup 0/C and in the pressure region of 20 to 80 bar. Raising the CO partial pressure accelerated the deactivation whereas raising the H/sub 2/ partial pressure slowed it down. An influence of the temperature could not be clearly recognized. The deactivation got slower with greater dwell time and larger degree of conversion. Two hypotheses to explain the deactivation are given.

Adsorption of cadmium ions on nickel surface skeleton catalysts and its effect on reaction of cathodic hydrogen evolution

International Nuclear Information System (INIS)

Korovin, N.V.; Udris, E.Ya.; Savel'eva, O.N.

1986-01-01

Cadmium adsorption from different concentration CdSO 4 solutions on nickel surface skeleton catalysts (Ni ssc ) is studied by recording of polarization and potentiodynamic curves using electron microscopy and X-ray spectrometry. Main regularities of cadmium adsorption on Ni ssc are shown to be similar to those on smooth and skeleton nickel. A conclusion is drawn that increase of catalytic activity in reaction of cathodic hydrogen evolution from alkali solutions of Ni ssc base electrodes after their treatment in solutions containing Cd 2+ ions is due to irreversible desorption of strongly and averagely bound hydrogen from electrode surface at cadmium adsorption on them

The Difference Se Makes: A Bio-Inspired Dppf-Supported Nickel Selenolate Complex Boosts Dihydrogen Evolution with High Oxygen Tolerance.

Science.gov (United States)

Pan, Zhong-Hua; Tao, Yun-Wen; He, Quan-Feng; Wu, Qiao-Yu; Cheng, Li-Ping; Wei, Zhan-Hua; Wu, Ji-Huai; Lin, Jin-Qing; Sun, Di; Zhang, Qi-Chun; Tian, Dan; Luo, Geng-Geng

2018-06-12

Inspired by the metal active sites of [NiFeSe]-hydrogenases, a dppf-supported nickel(II) selenolate complex (dppf=1,1'-bis(diphenylphosphino)ferrocene) shows high catalytic activity for electrochemical proton reduction with a remarkable enzyme-like H 2 evolution turnover frequency (TOF) of 7838 s -1 under an Ar atmosphere, which markedly surpasses the activity of a dppf-supported nickel(II) thiolate analogue with a low TOF of 600 s -1 . A combined study of electrochemical experiments and DFT calculations shed light on the catalytic process, suggesting that selenium atom as a bio-inspired proton relay plays a key role in proton exchange and enhancing catalytic activity of H 2 production. For the first time, this type of Ni selenolate-containing electrocatalyst displays a high degree of O 2 and H 2 tolerance. Our results should encourage the development of the design of highly efficient oxygen-tolerant Ni selenolate molecular catalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Screening of Catalysts for Hydrodeoxygenation of Phenol as Model Compound for Bio-oil

DEFF Research Database (Denmark)

Mortensen, Peter Mølgaard; Grunwaldt, Jan-Dierk; Jensen, Peter Arendt

2013-01-01

Four groups of catalysts have been tested for hydrodeoxygenation (HDO) of phenol as a model compound of bio-oil, including: oxide catalysts, methanol synthesis catalysts, reduced noble metal catalysts, and reduced non-noble metal catalysts. In total 23 different catalysts were tested at 100 bar H2...... and 275 °C in a batch reactor. The experiments showed that none of the tested oxides and methanol synthesis catalysts had any significant activity for phenol HDO at the given conditions, which were linked to their inability to hydrogenate the phenol. HDO of phenol over reduced metal catalysts could...... on a carbon support, but more active than the carbon supported noble metal catalysts when supported on ZrO2. This observation indicates that the nickel based catalysts require a metal oxide as carrier on which the activation of the phenol for the hydrogenation can take place through heterolytic dissociation...

Extended X-ray absorption fine structure and X-ray diffraction studies on supported Ni catalysts

International Nuclear Information System (INIS)

Aldea, N.; Marginean, P.; Yaning, Xie; Tiandou, Hu; Tao, Liu; Wu, Zhongua; ZhenYa, Dai

1999-01-01

In the first part of this paper, we present a study based on EXAFS spectroscopy. This method can yield structural information about the local environment around a specific atomic constituent in the amorphous materials, the location and chemical state of any catalytic atom on any support or point defect structures, in alloys and composites. EXAFS is a specific technique of the scattering of X-ray on materials. The present study is aimed toward elucidation of the local structure of Ni atoms and their interaction with oxide support. The second goal of the paper consists in X-ray diffraction on the same samples. X-ray diffraction method that is capable to determine average particle size, microstrains, probability of faults as well as particle size distribution function of supported Ni catalysts is presented. The method is based on the Fourier analysis of a single X-Ray diffraction profile. The results obtained on supported nickel catalysts, which are used in H/D isotopic exchange reactions are reported. The global structure is obtained with a new fitting method based on the Generalised Fermi Function facilities for approximation and Fourier transform of the experimental X-Ray line profiles. Both types of measurements were performed on Beijing Synchrotron Radiation Facilities (BSRF). (authors)

Catalyst support structure, catalyst including the structure, reactor including a catalyst, and methods of forming same

Science.gov (United States)

Van Norman, Staci A.; Aston, Victoria J.; Weimer, Alan W.

2017-05-09

Structures, catalysts, and reactors suitable for use for a variety of applications, including gas-to-liquid and coal-to-liquid processes and methods of forming the structures, catalysts, and reactors are disclosed. The catalyst material can be deposited onto an inner wall of a microtubular reactor and/or onto porous tungsten support structures using atomic layer deposition techniques.

Predicting catalyst-support interactions between metal nanoparticles and amorphous silica supports

Science.gov (United States)

Ewing, Christopher S.; Veser, Götz; McCarthy, Joseph J.; Lambrecht, Daniel S.; Johnson, J. Karl

2016-10-01

Metal-support interactions significantly affect the stability and activity of supported catalytic nanoparticles (NPs), yet there is no simple and reliable method for estimating NP-support interactions, especially for amorphous supports. We present an approach for rapid prediction of catalyst-support interactions between Pt NPs and amorphous silica supports for NPs of various sizes and shapes. We use density functional theory calculations of 13 atom Pt clusters on model amorphous silica supports to determine linear correlations relating catalyst properties to NP-support interactions. We show that these correlations can be combined with fast discrete element method simulations to predict adhesion energy and NP net charge for NPs of larger sizes and different shapes. Furthermore, we demonstrate that this approach can be successfully transferred to Pd, Au, Ni, and Fe NPs. This approach can be used to quickly screen stability and net charge transfer and leads to a better fundamental understanding of catalyst-support interactions.

Strategies for improving the performance and stability of Ni-based catalysts for reforming reactions.

Science.gov (United States)

Li, Shuirong; Gong, Jinlong

2014-11-07

Owing to the considerable publicity that has been given to petroleum related economic, environmental, and political problems, renewed attention has been focused on the development of highly efficient and stable catalytic materials for the production of chemical/fuel from renewable resources. Supported nickel nanoclusters are widely used for catalytic reforming reactions, which are key processes for generating synthetic gas and/or hydrogen. New challenges were brought out by the extension of feedstock from hydrocarbons to oxygenates derivable from biomass, which could minimize the environmental impact of carbonaceous fuels and allow a smooth transition from fossil fuels to a sustainable energy economy. This tutorial review describes the recent efforts made toward the development of nickel-based catalysts for the production of hydrogen from oxygenated hydrocarbons via steam reforming reactions. In general, three challenges facing the design of Ni catalysts should be addressed. Nickel nanoclusters are apt to sinter under catalytic reforming conditions of high temperatures and in the presence of steam. Severe carbon deposition could also be observed on the catalyst if the surface carbon species adsorbed on metal surface are not removed in time. Additionally, the production of hydrogen rich gas with a low concentration of CO is a challenge using nickel catalysts, which are not so active in the water gas shift reaction. Accordingly, three strategies were presented to address these challenges. First, the methodologies for the preparation of highly dispersed nickel catalysts with strong metal-support interaction were discussed. A second approach-the promotion in the mobility of the surface oxygen-is favored for the yield of desired products while promoting the removal of surface carbon deposition. Finally, the process intensification via the in situ absorption of CO2 could produce a hydrogen rich gas with low CO concentration. These approaches could also guide the design

Designing Pd-based supported bimetallic catalysts for environmental applications

OpenAIRE

Nowicka, Ewa; Meenakshisundaram, Sankar

2018-01-01

Supported bimetallic nanoparticulate catalysts are an important class of heterogeneous catalysts for many reactions including selective oxidation, hydrogenation/hydrogenolysis, reforming, biomass conversion reactions, and many more. The activity, selectivity, and stability of these catalysts depend on their structural features including particle size, composition, and morphology. In this review, we present important structural features relevant to supported bimetallic catalysts focusing on Pd...

Thermal and electrochemical stability of tungsten carbide catalyst supports

Energy Technology Data Exchange (ETDEWEB)

Chhina, H. [Ballard Power Systems, 9000 Glenlyon Parkway, Burnaby, BC (Canada); Department of Materials Engineering, University of British Columbia, Vancouver, BC (Canada); Campbell, S. [Ballard Power Systems, 9000 Glenlyon Parkway, Burnaby, BC (Canada); Kesler, O. [Department of Mechanical Engineering, University of British Columbia, Vancouver, BC (Canada)

2007-02-10

The thermal and electrochemical stability of tungsten carbide (WC), with and without a catalyst dispersed on it, have been investigated to evaluate the potential suitability of the material as an oxidation-resistant catalyst support. Standard techniques currently used to disperse Pt on carbon could not be used to disperse Pt on WC, so an alternative method was developed and used to disperse Pt on both commercially available WC and on carbon for comparison of stability. Electrochemical testing was performed by applying oxidation cycles between +0.6 V and +1.8 V to the support-catalyst material combinations and monitoring the activity of the supported catalyst over 100 oxidation cycles. Comparisons of activity change with cumulative oxidation cycles were made between C and WC supports with comparable loadings of catalyst by weight, solid volume, and powder volume. WC was found to be more thermally and electrochemically stable than currently used carbon support material Vulcan XC-72R. However, further optimization of the particle sizes and dispersion of Pt/WC catalyst/support materials and of comparison standards between new candidate materials and existing carbon-based supports are required. (author)

Effect study of the support in nickel and cobalt catalysts for obtaining hydrogen from ethanol steam reforming; Estudo do efeito do suporte em catalisadores de cobalto e niquel para obtencao de hidrogenio a partir da reforma a vapor do etanol

Energy Technology Data Exchange (ETDEWEB)

Silva, Sirlane Gomes da

2013-09-01

A range of oxide-supported metal catalysts have been investigated for the steam reforming of ethanol for the production of hydrogen and subsequent application in fuel cells. The catalysts were synthesized by the co-precipitation and internal gelification methods using cobalt and nickel as active metals supported on aluminum, zirconium, lanthanum and cerium oxides. After prepared and calcined at 550 C Masculine-Ordinal-Indicator the solids were fully characterized by different techniques such as X-rays diffraction(DRX), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy, nitrogen adsorption (B.E.T), temperature-programmed reduction in H2 (TPR-H2) and thermogravimetric analysis. The catalytic tests were performed in a monolithic quartz reactor and submitted to different thermodynamic conditions of steam reforming of ethanol at temperatures varying from 500 Masculine-Ordinal-Indicator C to 800 Masculine-Ordinal-Indicator C. The product gas streams from the reactor were analyzed by an on-line gas chromatograph. The cobalt/nickel catalyst supported on a ceria-lanthania mixture (Co{sub 10%} / Ni{sub 5%} - CeO{sub 2}La{sub 2}O{sub 3}) showed good catalytic performance in hydrogen selectivity reaching a concentration greater than 65%, when compared to other catalytic systems such as: Co{sub 10%} / Ni5% - CeO{sub 2}; Co{sub 10%} / Ni{sub 5%} - CeO{sub 2}ZrO{sub 2}; Co{sub 10%} / Ni{sub 5%} - ZrO{sub 2}; Co{sub 10%} / Ni{sub 5%} - La{sub 2}O{sub 3}; Co{sub 10%} / Ni{sub 5%} - CeO{sub 2}La{sub 2}O{sub 3}/K{sub 2%}; Co{sub 10}% / Ni{sub 5%} - CeO{sub 2}La{sub 2}O{sub 3} / Na{sub 2%}; Ni{sub 10%} / Co{sub 5%} - CeO{sub 2}La{sub 2}O{sub 3}; Co-Al{sub 2}O{sub 3} e Co-Al{sub 2}O{sub 3}CeO{sub 2}. (author)

Engineering New Catalysts for In-Process Elimination of Tars

Energy Technology Data Exchange (ETDEWEB)

Felix, Larry G. [Gas Technology Inst., Des Plaines, IL (United States)

2012-09-30

The key objective of this project was to develop a new and more efficient methodology for engineering and economically producing optimized robust catalysts for the reduction or elimination of tars in biomass gasification. Whereas current catalyst technology typically disposes thin layers of catalytically-active material onto rigid supports via wet chemistry-based methods, this project investigated novel thermal methods for directly incorporating catalytically active materials onto robust supports as well as novel approaches for incorporating catalytically active materials on and/or within an otherwise inert refractory support material which is then subsequently formed and processed to create a catalytically-active material on all exposed surfaces. Specifically, the focus of this engineered catalyst development was on materials which were derived from, or otherwise related to, olivine-like minerals, due to the inherent attrition resistance and moderate catalytic properties exhibited by natural olivine when used in a fluidized bed biomass gasifier. Task 1 of this project successfully demonstrated the direct thermal impregnation of catalytically-active materials onto an olivine substrate, with the production of a Ni-olivine catalyst. Nickel and nickel oxide were thermally impregnated onto an olivine substrate and when reduced were shown to demonstrate improved catalytic activity over the baseline olivine material and equal the tar-decomposing performance of Ni-olivine catalysts prepared by conventional wet impregnation. Task 2 involved coordination with our subcontracted project partners to further develop and characterize catalyst formulations and to optimize activity and production methods. Within this task, several significant new materials were developed. NexTech Materials developed a sintered ceramic nickel-magnesium-silicate catalyst that demonstrated superb catalytic activity and high resistance to deactivation by H2S. Alfred University developed both supported

Effects of P/Ni ratio and Ni content on performance of γ-Al{sub 2}O{sub 3}-supported nickel phosphides for deoxygenation of methyl laurate to hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Zhang, Zhena; Tang, Mingxiao; Chen, Jixiang, E-mail: jxchen@tju.edu.cn

2016-01-01

Graphical abstract: - Highlights: • The formation of AlPO{sub 4} was unfavorable for that of nickel phosphides. • The phase compositions of nickel phosphide depended on the amount of reduced P. • Catalytic activity was determined by surface Ni site density and catalyst acidity. • HDO pathway was promoted by increasing P/Ni ratio and Ni content. • Nickel phosphide gave much higher carbon yield and lower H{sub 2} consumption than Ni. - Abstract: γ-Al{sub 2}O{sub 3}-supported nickel phosphides (mNi-Pn) were prepared by the TPR method and tested for the deoxygenation of methyl laurate to hydrocarbons. The effects of the P/Ni ratio (n = 1.0–2.5) and Ni content (m = 5–15 wt.%) in the precursors on their structure and performance were investigated. Ni/γ-Al{sub 2}O{sub 3} was also studied for comparison. It was found that the formation of AlPO{sub 4} in the precursor inhibited the reduction of phosphate and so the formation of nickel phosphides. With increasing the P/Ni ratio and Ni content, the Ni, Ni{sub 3}P, Ni{sub 12}P{sub 5} and Ni{sub 2}P phases orderly formed, accompanying with the increases of their particle size and the amount of weak acid sites (mainly due to P-OH group), while the CO uptake and the amount of medium strong acid sites (mainly related to Ni sites) reached maximum on 10%Ni-P1.5. In the deoxygenation reaction, compared with Ni/γ-Al{sub 2}O{sub 3}, the mNi-Pn catalysts showed much lower activities for decarbonylation, C−C hydrogenolysis and methanation due to the ligand and ensemble effects of P. The conversion and the selectivity to n-C11 and n-C12 hydrocarbons achieved maximum on 10%Ni-P 2.0 for the 10%Ni-Pn catalysts and on 8%Ni-P2.0 for the mNi-P2.0 catalysts, while the turnover frequency (TOF) of methyl laurate mainly increased with the P/Ni ratio and Ni content. We propose that TOF was influenced by the nickel phosphide phases, the catalyst acidity and the particle size as well as the synergetic effect between the Ni site and

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.

Palm H-FAME Production through Partially Hydrogenation using Nickel/Carbon Catalyst to Increase Oxidation Stability

Directory of Open Access Journals (Sweden)

Ramayeni Elsa

2018-01-01

Full Text Available One of the methods to improve the oxidation stability of palm biodiesel is through partially hydrogenation. The production using Nickel/Carbon catalyst to speed up the reaction rate. Product is called Palm H-FAME (Hydrogenated FAME. Partial hydrogenation breaks the unsaturated bond on FAME (Fatty Acid Methyl Ester, which is a key component of the determination of oxidative properties. Changes in FAME composition by partial hydrogenation are predicted to change the oxidation stability so it does not cause deposits that can damage the injection system of diesel engine, pump system, and storage tank. Partial hydrogenation is carried out under operating conditions of 120 °C and 6 bar with 100:1, 100:3, 100:5, 100:10 % wt catalyst in the stirred batch autoclave reactor. H-FAME synthesis with 100:5 % wt Ni/C catalyst can decrease the iodine number which is the empirical measure of the number of unsaturated bonds from 91.78 to 82.38 (g-I2/100 g with an increase of oxidation stability from 585 to 602 minutes.

Sulfur Tolerant Magnesium Nickel Silicate Catalyst for Reforming of Biomass Gasification Products to Syngas

Directory of Open Access Journals (Sweden)

Scott L. Swartz

2012-04-01

Full Text Available Magnesium nickel silicate (MNS has been investigated as a catalyst to convert tars and light hydrocarbons to syngas (CO and H2 by steam reforming and CO2 reforming in the presence of H2S for biomass gasification process at NexTech Materials. It was observed that complete CH4 conversion could be achieved on MNS catalyst granules at 800–900 °C and a space velocity of 24,000 mL/g/h in a simulated biomass gasification stream. Addition of 10–20 ppm H2S to the feed had no apparent impact on CH4 conversion. The MNS-washcoated monolith also showed high activities in converting methane, light hydrocarbons and tar to syngas. A 1200 h test without deactivation was achieved on the MNS washcoated monolith in the presence of H2S and/or NH3, two common impurities in gasified biomass. The results indicate that the MNS material is a promising catalyst for removal of tar and light hydrocarbons from biomass gasified gases, enabling efficient use of biomass to produce power, liquid fuels and valuable chemicals.

Nickel catalyst supported on magnesium and zinc aluminates (MgAl{sub 2}O{sub 4} and ZnAl{sub 2}O{sub 4}) spinels for dry reforming of methane

Energy Technology Data Exchange (ETDEWEB)

Araujo, L.C.B. de; Melo, D.M. de A.; Melo, M.A. de F.; Barros, J.M. de F.; Braga, R.M.; Costa, C. de C.; Rodrigues, G., E-mail: ieda.garcia@pq.cnpq.br [Universidade Federal da Paraiba (LACOM/UFPB), Joao Pessoa, PB (Brazil). Dept. de Quimica

2017-01-15

Materials such as MgAl{sub 2}O{sub 4} and ZnAl{sub 2}O{sub 4} assessed in the reaction of dry reforming of methane to produce syngas were synthesized by microwave-assisted combustion method using urea as fuel. Samples of synthesized oxides were calcined at 800 °C for 2 h and impregnated with 5% nickel. The impregnated samples were calcined at 850 °C for 4 h to obtain the desired phases. The results of the catalytic tests showed that the catalysts are active for the reaction of dry reforming of methane, and the catalyst that showed the best performance for methane conversion was 5% Ni/MgAl{sub 2}O{sub 4} calcined at 850 °C/4 h. (author)

CO methanation over supported bimetallic Ni-Fe catalysts: From computational studies towards catalyst optimization

DEFF Research Database (Denmark)

Kustov, Arkadii; Frey, Anne Mette; Larsen, Kasper Emil

2007-01-01

with compositions 25Fe75Ni and 50Fe50Ni showed significantly better activity and in some cases also a higher selectivity to methane compared with the traditional monometallic Ni and Fe catalysts. A catalyst with composition 25Fe75Ni was found to be the most active in CO hydrogenation for the MgAl2O4 support at low...... metal loadings. At high metal concentrations, the maximum for the methanation activity was found for catalysts with composition 50Ni50Fe both on the MgAl2O4 and Al2O3 supports. This difference can be attributed to a higher reducibility of the constituting metals with increasing metal concentration......DFT calculations combined with a computational screening method have previously shown that bimetallic Ni-Fe alloys should be more active than the traditional Ni-based catalyst for CO methanation. That was confirmed experimentally for a number of bimetallic Ni-Fe catalysts supported on MgAl2O4. Here...

Pd supported on carbon containing nickel, nitrogen and sulfur for ethanol electrooxidation.

Science.gov (United States)

Yang, Zi-Rui; Wang, Shang-Qing; Wang, Jing; Zhou, Ai-Ju; Xu, Chang-Wei

2017-11-13

Carbon material containing nickel, nitrogen and sulfur (Ni-NSC) has been synthesized using metal-organic frameworks (MOFs) as precursor by annealing treatment with a size from 200 to 300 nm. Pd nanoparticles supported on the Ni-NSC (Pd/Ni-NSC) are used as electrocatalysts for ethanol oxidation in alkaline media. Due to the synergistic effect between Pd and Ni, S, N, free OH radicals can form on the surface of Ni, N and S atoms at lower potentials, which react with CH 3 CO intermediate species on the Pd surface to produce CH 3 COO - and release the active sites. On the other hand, the stronger binding force between Pd and co-doped N and S is responsible for enhancing dispersion and preventing agglomeration of the Pd nanoparticles. The Pd(20 wt%)/Ni-NSC shows better electrochemical performance of ethanol oxidation than the traditional commercial Pd(20 wt%)/C catalyst. Onset potential on the Pd(20 wt%)/Ni-NSC electrode is 36 mV more negative compared with that on the commercial Pd(20 wt%)/C electrode. The Pd(20 wt%)/Ni-NSC in this paper demonstrates to have excellent electrocatalytic properties and is considered as a promising catalyst in alkaline direct ethanol fuel cells.

From fundamental studies of reactivity on single crystals to the design of catalysts

Science.gov (United States)

H. Larsen, Jane; Chorkendorff, Ib

One of the prominent arguments for performing surface science studies have for many years been to improve and design new and better catalysts. Although surface science has provided the fundamental framework and tools for understanding heterogeneous catalysis until now there have been extremely few examples of actually designing new catalysts based solely on surface science studies. In this review, we shall demonstrate how a close collaboration between different fundamental disciplines like structural-, theoretical-and reactivity-studies of surfaces as well as a strong interaction with industry can have strong synergetic effects and how this was used to develop a new catalyst. As so often before the studies reviewed here were not initiated with the objective to solve a specific problem, but realizing that a new class of very stable two-dimensional alloys could be synthesized from otherwise immiscible metals made it possible to present a new solution to a specific problem in the industrial catalysis relating to methane activation in the steam reforming process. Methane is the main constituent of natural gas and it is an extremely important raw material for many large scale chemical processes such as production of hydrogen, ammonia, and methanol. In the steam reforming process methane and water are converted into a mixture of mainly hydrogen and carbon monoxide, the so-called synthesis gas. Industrially the steam reforming process usually takes place over a catalyst containing small nickel crystallites highly dispersed on a porous support material like aluminum/magnesium oxides in order to achieve a high active metal area. There is a general consensus that the rate limiting step of this process is the dissociative sticking of methane on the nickel surface. Driven by the desire to understand this step and hopefully be able to manipulate the reactivity, a large number of investigations of the methane/nickel interaction have been performed using nickel single crystals as

Catalytic Hydrolysis of Ammonia Borane by Cobalt Nickel Nanoparticles Supported on Reduced Graphene Oxide for Hydrogen Generation

Directory of Open Access Journals (Sweden)

Yuwen Yang

2014-01-01

Full Text Available Well dispersed magnetically recyclable bimetallic CoNi nanoparticles (NPs supported on the reduced graphene oxide (RGO were synthesized by one-step in situ coreduction of aqueous solution of cobalt(II chloride, nickel (II chloride, and graphite oxide (GO with ammonia borane (AB as the reducing agent under ambient condition. The CoNi/RGO NPs exhibits excellent catalytic activity with a total turnover frequency (TOF value of 19.54 mol H2 mol catalyst−1 min−1 and a low activation energy value of 39.89 kJ mol−1 at room temperature. Additionally, the RGO supported CoNi NPs exhibit much higher catalytic activity than the monometallic and RGO-free CoNi counterparts. Moreover, the as-prepared catalysts exert satisfying durable stability and magnetically recyclability for the hydrolytic dehydrogenation of AB, which make the practical reusing application of the catalysts more convenient. The usage of the low-cost, easy-getting catalyst to realize the production of hydrogen under mild condition gives more confidence for the application of ammonia borane as a hydrogen storage material. Hence, this general method indicates that AB can be used as both a potential hydrogen storage material and an efficient reducing agent, and can be easily extended to facile preparation of other RGO-based metallic systems.

Supported chromium-molybdenum and tungsten sulfide catalysts

International Nuclear Information System (INIS)

Chianelli, R.R.; Jacobson, A.J.; Young, A.R.

1988-01-01

This patent describes the process for preparing a supported hydroprocessing catalyst. The process comprising compositing a quantity of a particulate, porous catalyst support material comprising one or more refactory oxides with one or more catalyst precursor salts and heating the composite at elevated temperature of at least about 200/sup 0/C up to about 600/sup 0/, in the presence of a sulfur-bearing compound in an amount whereby sulfur in the form of the sulfur-bearing compound in an amount whereby sulfur in the form of the sulfur bearing compound is present in excess of that contained in the catalyst precursor and under oxygen-free conditions for a time sufficient to form the catalyst. The catalyst precursor salt contains a tetrathiometallate anion of Mo, W or mixture therof and a cation comprising trivalent chromium or a mixture of trivalent chromium with one or more divalent promoter metals selected from the group consisting of Fe, Ni, Co, Mn, Cu and a mixture thereof wherein the trivalent chromium and divalent promoter metals are chelated by at least one neutral, nitrogen-containing polydentate ligand, L

Heterogenization of Homogeneous Catalysts: the Effect of the Support

Energy Technology Data Exchange (ETDEWEB)

Earl, W.L.; Ott, K.C.; Hall, K.A.; de Rege, F.M.; Morita, D.K.; Tumas, W.; Brown, G.H.; Broene, R.D.

1999-06-29

We have studied the influence of placing a soluble, homogeneous catalyst onto a solid support. We determined that such a 'heterogenized' homogeneous catalyst can have improved activity and selectivity for the asymmetric hydrogenation of enamides to amino acid derivatives. The route of heterogenization of RhDuPhos(COD){sup +} cations occurs via electrostatic interactions with anions that are capable of strong hydrogen bonding to silica surfaces. This is a novel approach to supported catalysis. Supported RhDuPhos(COD){sup +} is a recyclable, non-leaching catalyst in non-polar media. This is one of the few heterogenized catalysts that exhibits improved catalytic performance as compared to its homogeneous analog.

57Fe Moessbauer Studies in Mo-Fe Supported Catalysts

International Nuclear Information System (INIS)

Castelao-Dias, M.; Costa, B. F. O.; Quinta-Ferreira, R. M.

2001-01-01

Industrially, the Mo-Fe catalysts used in the selective oxidation of methanol to formaldehyde can rapidly deactivate. The use of support materials may reduce the high temperatures in the catalytic bed and/or increase thermal and mechanical resistance. However, during the preparation of these catalysts, or even during reaction conditions, the active species may react with the support material losing their catalytic activity. In this work silica, silicium carbide and titania were studied as supported catalysts by Moessbauer spectroscopy which proved to be a useful technique in the choice of supported materials

Polypropylene obtained through zeolite supported catalysts

Directory of Open Access Journals (Sweden)

Queli C. Bastos

2004-01-01

Full Text Available Propylene polymerizations were carried out with f2C(Flu(CpZrCl2 and SiMe2(Ind2ZrCl2 catalysts supported on silica, zeolite sodic mordenite (NaM and acid mordenite (HM. The polymerizations were performed at different temperatures and varying aluminium/zirconium molar ratios ([Al]/[Zr]. The effect of these reaction parameters on the catalyst activity was investigated using a proposed statistical experimental planning. In the case of f2C(Flu(CpZrCl2, SiO2 and NaM were used as support and the catalyst performance evaluated using toluene and pentane as polymerization solvent. The molecular weight, molecular weight distribution, melting point and crystallinity of the polymers were examined. The results indicate very high activities for the syndiospecific heterogeneous system. Also, the polymers obtained had superior Mw and stereoregularity.

Polypropylene obtained through zeolite supported catalysts

International Nuclear Information System (INIS)

Bastos, Queli C.; Marques, Maria de Fatima V.

2004-01-01

Propylene polymerizations were carried out with φ 2 C(Flu)(Cp)ZrCl 2 and SiMe 2 (Ind)2ZrCl 2 catalysts supported on silica, zeolite sodic mordenite (NaM) and acid mordenite (HM). The polymerizations were performed at different temperatures and varying aluminium/zirconium molar ratios ([Al]/[Zr]). The effect of these reaction parameters on the catalyst activity was investigated using a proposed statistical experimental planning. In the case of f 2 C(Flu)(Cp)ZrCl 2 , SiO 2 and NaM were used as support and the catalyst performance evaluated using toluene and pentane as polymerization solvent. The molecular weight, molecular weight distribution, melting point and crystallinity of the polymers were examined. The results indicate very high activities for the syndiospecific heterogeneous system. Also, the polymers obtained had superior Mw and stereo regularity. (author)

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(...

Catalyst support effects on hydrogen spillover

Science.gov (United States)

Karim, Waiz; Spreafico, Clelia; Kleibert, Armin; Gobrecht, Jens; Vandevondele, Joost; Ekinci, Yasin; van Bokhoven, Jeroen A.

2017-01-01

Hydrogen spillover is the surface migration of activated hydrogen atoms from a metal catalyst particle, on which they are generated, onto the catalyst support. The phenomenon has been much studied and its occurrence on reducible supports such as titanium oxide is established, yet questions remain about whether hydrogen spillover can take place on nonreducible supports such as aluminium oxide. Here we use the enhanced precision of top-down nanofabrication to prepare controlled and precisely tunable model systems that allow us to quantify the efficiency and spatial extent of hydrogen spillover on both reducible and nonreducible supports. We place multiple pairs of iron oxide and platinum nanoparticles on titanium oxide and aluminium oxide supports, varying the distance between the pairs from zero to 45 nanometres with a precision of one nanometre. We then observe the extent of the reduction of the iron oxide particles by hydrogen atoms generated on the platinum using single-particle in situ X-ray absorption spectromicroscopy applied simultaneously to all particle pairs. The data, in conjunction with density functional theory calculations, reveal fast hydrogen spillover on titanium oxide that reduces remote iron oxide nanoparticles via coupled proton-electron transfer. In contrast, spillover on aluminium oxide is mediated by three-coordinated aluminium centres that also interact with water and that give rise to hydrogen mobility competing with hydrogen desorption; this results in hydrogen spillover about ten orders of magnitude slower than on titanium oxide and restricted to very short distances from the platinum particle. We anticipate that these observations will improve our understanding of hydrogen storage and catalytic reactions involving hydrogen, and that our approach to creating and probing model catalyst systems will provide opportunities for studying the origin of synergistic effects in supported catalysts that combine multiple functionalities.

Principal component analysis of NEXAFS spectra for molybdenum speciation in hydrotreating catalysts

International Nuclear Information System (INIS)

Faro Junior, Arnaldo da C.; Rodrigues, Victor de O.; Eon, Jean-G.; Rocha, Angela S.

2010-01-01

Bulk and supported molybdenum based catalysts, modified by nickel, phosphorous or tungsten were studied by NEXAFS spectroscopy at the Mo L III and L II edges. The techniques of principal component analysis (PCA) together with a linear combination analysis (LCA) allowed the detection and quantification of molybdenum atoms in two different coordination states in the oxide form of the catalysts, namely tetrahedral and octahedral coordination. (author)

Interfacial charge distributions in carbon-supported palladium catalysts

DEFF Research Database (Denmark)

Rao, Radhika G.; Blume, Raoul; Hansen, Thomas Willum

2017-01-01

Controlling the charge transfer between a semiconducting catalyst carrier and the supported transition metal active phase represents an elite strategy for fine turning the electronic structure of the catalytic centers, hence their activity and selectivity. These phenomena have been theoretically...... and experimentally elucidated for oxide supports but remain poorly understood for carbons due to their complex nanoscale structure. Here, we combine advanced spectroscopy and microscopy on model Pd/C samples to decouple the electronic and surface chemistry effects on catalytic performance. Our investigations reveal...... treatments can be used to tune the interfacial charge distribution, hereby providing a strategy to rationally design carbon-supported catalysts.Control over charge transfer in carbon-supported metal nanoparticles is essential for designing new catalysts. Here, the authors show that thermal treatments...

Nitrogen-doped carbon nanotubes as a metal catalyst support

CSIR Research Space (South Africa)

Mabena, LF

2011-05-01

Full Text Available ., which are among the most commonly used heterogeneous catalyst supports (Mart??nez-Me?ndez et al. 2006). Catalyst activity depends on the particle size and appropriate dis- tance between each particle. These catalysts deposited on a support... supported Pt electrodes. Appl Catal B Environ 80:286?295 Maldonado S, Morin S, Stevenson KJ (2006) Structure, composition, and chemical reactivity of carbon nanotubes by selective nitrogen doping. Carbon 44:1429?1437 Mart??nez-Me?ndez S, Henr??quez Y...

SiC nanocrystals as Pt catalyst supports for fuel cell applications

DEFF Research Database (Denmark)

Dhiman, Rajnish; Morgen, Per; Skou, E.M.

2013-01-01

A robust catalyst support is pivotal to Proton Exchange Membrane Fuel Cells (PEMFCs) to overcome challenges such as catalyst support corrosion, low catalyst utilization and overall capital cost. SiC is a promising candidate material which could be applied as a catalyst support in PEMFCs. Si...... on the nanocrystals of SiC-SPR and SiC-NS by the polyol method. The SiC substrates are subjected to an acid treatment to introduce the surface groups, which help to anchor the Pt nano-catalysts. These SiC based catalysts have been found to have a higher electrochemical activity than commercially available Vulcan...... based catalysts (BASF & HISPEC). These promising results signal a new era of SiC based catalysts for fuel cell applications....

Protein Scaffolding for Small Molecule Catalysts

Energy Technology Data Exchange (ETDEWEB)

Baker, David [Univ. of Washington, Seattle, WA (United States)

2014-09-14

We aim to design hybrid catalysts for energy production and storage that combine the high specificity, affinity, and tunability of proteins with the potent chemical reactivities of small organometallic molecules. The widely used Rosetta and RosettaDesign methodologies will be extended to model novel protein / small molecule catalysts in which one or many small molecule active centers are supported and coordinated by protein scaffolding. The promise of such hybrid molecular systems will be demonstrated with the nickel-phosphine hydrogenase of DuBois et. al.We will enhance the hydrogenase activity of the catalyst by designing protein scaffolds that incorporate proton relays and systematically modulate the local environment of the catalyticcenter. In collaboration with DuBois and Shaw, the designs will be experimentally synthesized and characterized.

Catalytic performance of Ni/MgO catalyst in methane dry reforming

Science.gov (United States)

Al-Swai, Basem M.; Osman, N. B.; Abdullah, Bawadi

2017-10-01

Methane dry reforming to synthesis gas over nickel catalysts supported on magnesium oxide has been studied. The support was prepared via co-precipitation method using ammonia solution (20 wt% in water) as the precipitating agent. 10 wt% of Ni metal was impregnated to form Ni/MgO catalyst. The prepared catalyst was characterized by different techniques, such as XRD, BET, SEM, and TGA analysis. The effect of reaction conditions on the conversions of CH4 and CO2, selectivity of H2 and CO, and carbon deposition were investigated in a tabular furnace reactor. The catalyst afforded as high as 93% CH4 conversion at 900 °C. The catalyst has also shown excellent stability during reaction at relatively higher space velocity (1.8×104 ml g-1 h-1) and 800 °C reaction temperature. TGA characterization of spent catalyst has shown lesser magnitude of carbon deposition on the surface of the catalyst at 900 °C.

Attrition Resistant Fischer-Tropsch Catalysts Based on FCC Supports

Energy Technology Data Exchange (ETDEWEB)

Adeyiga, Adeyinka

2010-02-05

Commercial spent fluid catalytic cracking (FCC) catalysts provided by Engelhard and Albemarle were used as supports for Fe-based catalysts with the goal of improving the attrition resistance of typical F-T catalysts. Catalysts with the Ruhrchemie composition (100 Fe/5 Cu/4.2 K/25 spent FCC on mass basis) were prepared by wet impregnation. XRD and XANES analysis showed the presence of Fe{sub 2}O{sub 3} in calcined catalysts. FeC{sub x} and Fe{sub 3}O{sub 4} were present in the activated catalysts. The metal composition of the catalysts was analyzed by ICP-MS. F-T activity of the catalysts activated in situ in CO at the same conditions as used prior to the attrition tests was measured using a fixed bed reactor at T = 573 K, P = 1.38 MPa and H{sub 2}:CO ratio of 0.67. Cu and K promoted Fe supported over Engelhard provided spent FCC catalyst shows relatively good attrition resistance (8.2 wt% fines lost), high CO conversion (81%) and C{sub 5}+ hydrocarbons selectivity (18.3%).

Hydrogenation of carbon monoxide over supported palladium catalysts

Energy Technology Data Exchange (ETDEWEB)

Fujimoto, K.; Hashimoto, H.; Kunugi, T.

1978-03-01

An alumina-supported 2% palladium catalyst had higher activity for carbon monoxide hydrogenation than a silica-supported 2% palladium catalyst, at 250/sup 0/-400/sup 0/C and 1 atm. The addition of lanthanum oxide or thorium oxide, but not of potassium oxide, to the silica-supported catalyst increased the conversion at 350/sup 0/C from 1.1% to 81.0% with a selectivity of 56.1% for methane, 1.4% for C/sub 2/ compounds, 0.1% for C/sub 3/ compounds, and 42.5% for carbon dioxide. Temperature-programed desorption of carbon monoxide in a hydrogen stream showed that of two desorption peaks observed for carbon monoxide, the one at higher temperature corresponded to the carbon monoxide species which hydrogenates to methane and that the area of this peak increased with increasing thorium content of the catalyst. Graphs, tables, and 12 references.

Zircon Supported Copper Catalysts for the Steam Reforming of Methanol

Science.gov (United States)

Widiastri, M.; Fendy, Marsih, I. N.

2008-03-01

Steam reforming of methanol (SRM) is known as one of the most favorable catalytic processes for producing hydrogen. Current research on zirconia, ZrO2 supported copper catalyst revealed that CuO/ZrO2 as an active catalyst for the SRM. Zircon, ZrSiO4 is available from the by-product of tin mining. In the work presented here, the catalytic properties of CuO/ZrSiO4 with various copper oxide compositions ranging from 2.70% (catalyst I), 4.12% (catalyst II), and 7.12%-mass (catalyst III), synthesized by an incipient wetness impregnation technique, were investigated to methanol conversion, selectivity towards CO formation, and effect of ZnO addition (7.83%CuO/8.01%ZnO/ZrSiO4 = catalyst V). The catalytic activity was obtained using a fixed bed reactor and the zircon supported catalyst activity was compared to those of CuO/ZnO/Al2O3 catalyst (catalyst IV) and commercial Kujang LTSC catalyst. An X-ray powder diffraction (XRD) analysis was done to identify the abundant phases of the catalysts. The catalysts topography and particle diameter were measured with scanning electron microscopy (SEM) and composition of the catalysts was measured by SEM-EDX, scanning electron microscope-energy dispersive using X-ray analysis. The results of this research provide information on the possibility of using zircon (ZrSiO4) as solid support for SRM catalysts.

Effect of nickel introduced by electroplating on pyrocarbon deposition of carbon-fiber preforms

Directory of Open Access Journals (Sweden)

Ren Yancai

2014-08-01

Full Text Available In order to improve the deposition rate and microstructure of pyrocarbon, nickel was introduced by electroplating on carbon fibers and used as a catalyst during the deposition of pyrocarbon at 1000 °C using methane as a precursor gas. The distribution of nickel catalyst and the microstructure of pyrocarbon were characterized by scanning electron microscopy (SEM, energy dispersive spectroscopy (EDS, X-ray diffraction (XRD, and Raman micro-spectrometry. Results show that nano-sized nickel particles could be well distributed on carbon fibers and the pyrocarbon deposited catalytically had a smaller d002 value and a higher graphitization degree compared with that without catalyst. In addition, the deposition rate of pyrocarbon in each hour was measured. The deposition rate of pyrocarbon in the first hour was more than 10 times when carbon cloth substrates were doped with nickel catalysts as compared to the pure carbon cloths. The pyrocarbon gained by rapid deposition may include two parts, which are generation directly on the nickel catalyst and formation with the carbon nanofibers as crystal nucleus.

Support Functionalization To Retard Ostwald Ripening in Copper Methanol Synthesis Catalysts

NARCIS (Netherlands)

van den Berg, Roy; Parmentier, Tanja E.; Elkjaer, Christian F.; Gommes, Cedric J.; Sehested, Jens; Helveg, Stig; de Jongh, Petra E.; de Jong, Krijn P.

A main reason for catalyst deactivation in supported catalysts for methanol synthesis is copper particle growth. We have functionalized the support surface in order to suppress the formation and/or transport of mobile copper species and thereby catalyst deactivation. A Stober silica support was

Nickel metal with various morphologies: synthesis and performances for catalytic carbon dioxide reforming with methane.

Science.gov (United States)

Teabpinyok, Nopporn; Samingprai, Sutheerawat; Chareonpanich, Metta

2012-12-01

In this research, nickel metal of three different morphologies including nanostar, icosahedra, and microsphere structures were synthesized. It was found nanostar nickel revealed the Ni(111) crystallographic plane with particle size in the range of 150-200 nm and BET surface area of 13 m2/g. The icosahedra nickel also showed the Ni(111) crystallographic plane with larger particle size (300-400 nm) and BET surface area of 20 m2/g, whereas microsphere nickel exhibited the relatively large cluster size (approximately 3 microm) and BET surface area (114 m2/g) as a result of an aggregation of Ni(101) nanoplates. The obtained nickel catalysts were tested for the activity in carbon dioxide reforming with methane. Based on the similar specific surface area of catalysts, nanostar nickel showed the highest carbon dioxide and methane conversions due to its crystallographic structure. At 700 degrees C, nanostar nickel catalyst exhibited the highest carbon dioxide and methane conversions of 17.6 and 10.5 times higher than those of microsphere nickel catalyst, respectively.

Catalytic upgrading of oleic acid into biofuel using Mo modified zeolite supported Ni oxalate catalyst functionalized with fluoride ion

International Nuclear Information System (INIS)

Ayodele, O.B.; Abbas, Hazzim F.; Daud, Wan Mohd Ashri Wan

2014-01-01

Highlights: • Modification of zeolite with freshly prepared molybdenum oxalate. • Functionalization of Ni oxalate with HF and incorporation into Mo modified zeolite. • Characterization of synthesized Mo modified zeolite supported Ni oxalate catalyst. • Deoxygenation of oleic acid with the synthesized zeolite supported catalyst. • Reusability study on the synthesized zeolite supported catalyst. - Abstract: In this study, fluoride ion functionalized nickel oxalate supported on molybdenum modified zeolite (NiMoFOx/Zeol) catalyst was synthesized, characterized and tested on the hydrodeoxygenation (HDO) of oleic acid (OA) into paraffinic fuel. The NiMoFOx/Zeol characterization results confirmed the presence of both Ni and Mo as well as the formation of NiMoO 4 which is a highly HDO reactive specie at 2θ value of 43.6° according to the XRD result. NiMoFOx/Zeol also showed loss in crystallinity and reduction in the average particle size leading to increase in the pore volume and specific surface area due to the combined effects of fluoride ion presence, oxalic acid functionalization and calcination. The effect of temperature, pressure and NiMoFOx/Zeol loading studied showed that initial increase in their values increased the yield of the target fractions until some points where reduction was observed. The best observed experimental conditions to hydrodeoxygenate 40 g (∼45 mL) of OA into 75% n-C 18 and 23% i-C 18 were 360 °C, 30 mg NiMoFOx/Zeol loading and 20 bar using 100 mL H 2 /min. The presence of i-C 18 was due to the functionalization of the catalyst with fluoride ion. The catalyst reusability result displayed excellent qualities with marginal loss of only 2% in activity after third reuse due to the improved synthesis protocol that employed organometallic precursor. The results are strongly encouraging for further studies toward industrialization of HDO process

MOF-derived Co-doped nickel selenide/C electrocatalysts supported on Ni foam for overall water splitting

KAUST Repository

Ming, Fangwang; Liang, Hanfeng; Shi, Huanhuan; Xu, Xun; Mei, Gui; Wang, Zhoucheng

2016-01-01

It is of prime importance to develop dual-functional electrocatalysts with good activity for overall water splitting, which remains a great challenge. Herein, we report the synthesis of a Co-doped nickel selenide (a mixture of NiSe and NiSe)/C hybrid nanostructure supported on Ni foam using a metal-organic framework as the precursor. The resulting catalyst exhibits excellent catalytic activity toward the oxygen evolution reaction (OER), which only requires an overpotential of 275 mV to drive a current density of 30 mA cm. This overpotential is much lower than those reported for precious metal free OER catalysts. The hybrid is also capable of catalyzing the hydrogen evolution reaction (HER) efficiently. A current density of -10 mA cm can be achieved at 90 mV. In addition, such a hybrid nanostructure can achieve 10 and 30 mA cm at potentials of 1.6 and 1.71 V, respectively, along with good durability when functioning as both the cathode and the anode for overall water splitting in basic media.

MOF-derived Co-doped nickel selenide/C electrocatalysts supported on Ni foam for overall water splitting

KAUST Repository

Ming, Fangwang

2016-09-01

It is of prime importance to develop dual-functional electrocatalysts with good activity for overall water splitting, which remains a great challenge. Herein, we report the synthesis of a Co-doped nickel selenide (a mixture of NiSe and NiSe)/C hybrid nanostructure supported on Ni foam using a metal-organic framework as the precursor. The resulting catalyst exhibits excellent catalytic activity toward the oxygen evolution reaction (OER), which only requires an overpotential of 275 mV to drive a current density of 30 mA cm. This overpotential is much lower than those reported for precious metal free OER catalysts. The hybrid is also capable of catalyzing the hydrogen evolution reaction (HER) efficiently. A current density of -10 mA cm can be achieved at 90 mV. In addition, such a hybrid nanostructure can achieve 10 and 30 mA cm at potentials of 1.6 and 1.71 V, respectively, along with good durability when functioning as both the cathode and the anode for overall water splitting in basic media.

Effects of P/Ni ratio and Ni content on performance of γ-Al2O3-supported nickel phosphides for deoxygenation of methyl laurate to hydrocarbons

Science.gov (United States)

Zhang, Zhena; Tang, Mingxiao; Chen, Jixiang

2016-01-01

γ-Al2O3-supported nickel phosphides (mNi-Pn) were prepared by the TPR method and tested for the deoxygenation of methyl laurate to hydrocarbons. The effects of the P/Ni ratio (n = 1.0-2.5) and Ni content (m = 5-15 wt.%) in the precursors on their structure and performance were investigated. Ni/γ-Al2O3 was also studied for comparison. It was found that the formation of AlPO4 in the precursor inhibited the reduction of phosphate and so the formation of nickel phosphides. With increasing the P/Ni ratio and Ni content, the Ni, Ni3P, Ni12P5 and Ni2P phases orderly formed, accompanying with the increases of their particle size and the amount of weak acid sites (mainly due to P-OH group), while the CO uptake and the amount of medium strong acid sites (mainly related to Ni sites) reached maximum on 10%Ni-P1.5. In the deoxygenation reaction, compared with Ni/γ-Al2O3, the mNi-Pn catalysts showed much lower activities for decarbonylation, Csbnd C hydrogenolysis and methanation due to the ligand and ensemble effects of P. The conversion and the selectivity to n-C11 and n-C12 hydrocarbons achieved maximum on 10%Ni-P 2.0 for the 10%Ni-Pn catalysts and on 8%Ni-P2.0 for the mNi-P2.0 catalysts, while the turnover frequency (TOF) of methyl laurate mainly increased with the P/Ni ratio and Ni content. We propose that TOF was influenced by the nickel phosphide phases, the catalyst acidity and the particle size as well as the synergetic effect between the Ni site and acid site. Again, the hydrodeoxygenation pathway of methyl laurate was promoted with increasing P/Ni ratio and Ni content, ascribed to the phase change in the order of Ni, Ni3P, Ni12P5 and Ni2P in the prepared catalysts.

Hydrogenation of surface carbon on alumina-supported nickel

Energy Technology Data Exchange (ETDEWEB)

Mccarthy, J.G.; Wise, H.

1979-05-01

The methanation of carbon deposited by CO or ethylene decomposition on Girdler G-65 catalyst (25Vertical Bar3< nickel, 8Vertical Bar3< alkali, mostly CaO, 4Vertical Bar3< C as graphite, on alumina) was studied by temperature-programed desorption and temperature-programed surface reaction. Four types of carbon were identified: ..cap alpha..-carbon consisted of isolated carbon atoms bonded to nickel and reacting with hydrogen at 470/sup 0/ +/- 20/sup 0/K; ..gamma..-carbon was probably a bulk carbide, most likely Ni/sub 3/C, which had a reaction peak at 550/sup 0/K; ..beta..-carbon consisted of amorphous, polymerized carbon, which had a reaction peak at 680/sup 0/K; and an unreactive crystalline graphite-like species. The ..cap alpha..-form was thermally unstable and transformed into the ..beta..-form above 600/sup 0/K. Both ..cap alpha..- and ..beta..-forms slowly converted to inert graphite above 600/sup 0/K. The evidence suggested that synthesis gas methanation proceeds by dissociative adsorption of CO as the rate-determining step which forms a very reactive carbon adatom state (..cap alpha..') which converts to the ..cap alpha..-state in the absence of hydrogen and to methane in the presence of hydrogen.

Contribution to the study of the oxidation reaction of the carbon oxide in contact with catalysts issued from the decomposition of nickel hydro-aluminates at various temperatures

International Nuclear Information System (INIS)

Samaane, Mikhail

1966-01-01

Addressing the study of the oxidation reaction of carbon oxide which produces carbon dioxide, this research thesis reports the study of this reaction in presence of catalysts (2NiO + Al 2 O 3 , NiAl 2 O 4 and NiO + NiAl 2 O 4 ) issued from the decomposition of nickel hydro-aluminates at different temperatures. The first part describes experimental techniques and the nature of materials used in this study. The second part reports the study of the catalytic activity of the 2NiO+Al 2 O 3 catalyst during the oxidation of CO. Preliminary studies are also reported: structure and texture of nickel hydro-aluminate which is the raw material used to produce catalysts, activation of this compound to develop the catalytic activity in CO oxidation, chemisorption of CO, O 2 and CO 2 on the 2NiO+Al 2 O 3 solid, interaction of adsorbed gases at the solid surface, and kinetic study of the oxidation reaction. The third part reports the study of the catalytic activity in the oxidation reaction of CO of spinel catalysts (NiAl 2 O 4 and NiO+NiAl 2 O 4 ) obtained by calcination of nickel hydro-aluminates at high temperature. The formation of the spinel phase, the chemisorption of CO, O 2 and CO 2 on NiAl 2 O 4 , and the kinetic of the oxidation reaction are herein studied

Treatment of spent catalyst from the nitrogenous fertilizer industry-A review of the available methods of regeneration, recovery and disposal

International Nuclear Information System (INIS)

Singh, Bina

2009-01-01

Disposal of spent catalyst is a problem as it falls under the category of hazardous industrial waste. The recovery of metals from these catalysts is an important economic aspect as most of these catalysts are supported, usually on alumina/silica with varying percent of metal; metal concentration could vary from 2.5 to 20%. Metals like Ni, Mo, Co, Rh, Pt, Pd, etc., are widely used as a catalyst in chemical and petrochemical industries and fertilizer industries. They are generally supported on porous materials like alumina and silica through precipitation or impregnation processes. Many workers have adapted pyrometallurgy and Hydrometallurgy process for recovery of precious metals. Many workers have studied the recovery of nickel from a spent catalyst in an ammonia plant by leaching it in sulphuric acid solution (Hydrometallurgy). Ninety-nine percent of the nickel was recovered as nickel sulphate when the catalyst, having a particle size of 0.09 mm was dissolved in an 80% sulphuric acid solution for 50 min in at 70 deg. C. Many researcher have studied the extraction of metals from spent catalyst by roasting-extraction method (Pyrometallurgy). Chelating agents are the most effective extractants, which can be introduced in the soil washing fluid to enhance heavy metal extraction from contaminated soils. The advantages of chelating agents in soil cleanup include high efficiency of metal extraction, high thermodynamic stabilities of the metal complexes formed, good solubilities of the metal complexes, and low adsorption of the chelating agents on soils, But very few workers have attempted chelating agent to extract metals from spent catalyst.

Molecular metal catalysts on supports: organometallic chemistry meets surface science.

Science.gov (United States)

Serna, Pedro; Gates, Bruce C

2014-08-19

Recent advances in the synthesis and characterization of small, essentially molecular metal complexes and metal clusters on support surfaces have brought new insights to catalysis and point the way to systematic catalyst design. We summarize recent work unraveling effects of key design variables of site-isolated catalysts: the metal, metal nuclearity, support, and other ligands on the metals, also considering catalysts with separate, complementary functions on supports. The catalysts were synthesized with the goal of structural simplicity and uniformity to facilitate incisive characterization. Thus, they are essentially molecular species bonded to porous supports chosen for their high degree of uniformity; the supports are crystalline aluminosilicates (zeolites) and MgO. The catalytic species are synthesized in reactions of organometallic precursors with the support surfaces; the precursors include M(L)2(acetylacetonate)1-2, with M = Ru, Rh, Ir, or Au and the ligands L = C2H4, CO, or CH3. Os3(CO)12 and Ir4(CO)12 are used as precursors of supported metal clusters, and some such catalysts are made by ship-in-a-bottle syntheses to trap the clusters in zeolite cages. The simplicity and uniformity of the supported catalysts facilitate precise structure determinations, even in reactive atmospheres and during catalysis. The methods of characterizing catalysts in reactive atmospheres include infrared (IR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and nuclear magnetic resonance (NMR) spectroscopies, and complementary methods include density functional theory and atomic-resolution aberration-corrected scanning transmission electron microscopy for imaging of individual metal atoms. IR, NMR, XANES, and microscopy data demonstrate the high degrees of uniformity of well-prepared supported species. The characterizations determine the compositions of surface metal complexes and clusters, including the ligands and the metal-support

Characterization of composite metal-ceramic of nickel-oxide cerium doped gadolinium; Caracterizacao de compositos ceramica-metal de niquel e oxido de cerio dopado com gadolinio

Energy Technology Data Exchange (ETDEWEB)

Silva, M.L.A. da, E-mail: maria.andrade@pro.unifacs.br [Universidade Salvador (UNIFACS), BA (Brazil). Escola de Engenharia, Arquitetura e TI; Universidade Federal da Bahia (UFBA), BA (Brazil); Varela, M.C.R.S. [Universidade Federal da Bahia (UFBA), BA (Brazil)

2016-07-01

Composite nickel doped cerium oxide are used in SOFC anode materials. In this study we evaluated the effect of the presence of gadolinium on the properties of composite nickel and ceria and. The supports were synthesized by sol-gel method. The impregnation with nickel nitrate was taken sequentially, followed by calcination. The materials were characterized by X-ray diffraction, measurement of specific surface area, temperature programmed reduction, Raman spectroscopy. The presence of gadolinium retained the fluorite structure of ceria by forming a solid solution, also not influencing significantly on the specific surface area of the support. On the other hand, there was a decrease in the area catalysts, which can be attributed to sintering of nickel. Furthermore, addition of gadolinium favored the formation of intrinsic and extrinsic vacancies in cerium oxide, which leads to an increase in the ionic conductivity of the solid, desirable property for an SOFC anode catalyst. (author)

Morphology-Tuned Synthesis of Nickel Cobalt Selenides as Highly Efficient Pt-Free Counter Electrode Catalysts for Dye-Sensitized Solar Cells.

Science.gov (United States)

Qian, Xing; Li, Hongmei; Shao, Li; Jiang, Xiancai; Hou, Linxi

2016-11-02

In this work, morphology-tuned ternary nickel cobalt selenides based on different Ni/Co molar ratios have been synthesized via a simple precursor conversion method and used as counter electrode (CE) materials for dye-sensitized solar cells (DSSCs). The experimental facts and mechanism analysis clarified the possible growth process of product. It can be found that the electrochemical performance and structures of ternary nickel cobalt selenides can be optimized by tuning the Ni/Co molar ratio. Benefiting from the unique morphology and tunable composition, among the as-prepared metal selenides, the electrochemical measurements showed that the ternary nickel cobalt selenides exhibited a more superior electrocatalytic activity in comparison with binary Ni and Co selenides. In particular, the three-dimensional dandelion-like Ni 0.33 Co 0.67 Se microspheres delivered much higher power conversion efficiency (9.01%) than that of Pt catalyst (8.30%) under AM 1.5G irradiation.

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

Constrained Geometry Organotitanium Catalysts Supported on Nanosized Silica for Ethylene (co)Polymerization.

Science.gov (United States)

Li, Kuo-Tseng; Wu, Ling-Huey

2017-05-05

Supported olefin polymerization catalysts can prevent reactor-fouling problems and produce uniform polymer particles. Constrained geometry complexes (CGCs) have less sterically hindered active sites than bis-cyclopentadienyl metallocene catalysts. In the literature, micrometer-sized silica particles were used for supporting CGC catalysts, which might have strong mass transfer limitations. This study aims to improve the activity of supported CGC catalysts by using nanometer-sized silica. Ti[(C₅Me₄)SiMe₂(N t Bu)]Cl₂, a "constrained-geometry" titanium catalyst, was supported on MAO-treated silicas (nano-sized and micro-sized) by an impregnation method. Ethylene homo-polymerization and co-polymerization with 1-octene were carried out in a temperature range of 80-120 °C using toluene as the solvent. Catalysts prepared and polymers produced were characterized. For both catalysts and for both reactions, the maximum activities occurred at 100 °C, which is significantly higher than that (60 °C) reported before for supported bis-cyclopentadienyl metallocene catalysts containing zirconium, and is lower than that (≥140 °C) used for unsupported Ti[(C₅Me₄)SiMe₂(N t Bu)]Me₂ catalyst. Activities of nano-sized catalyst were 2.6 and 1.6 times those of micro-sized catalyst for homopolymerization and copolymerization, respectively. The former produced polymers with higher crystallinity and melting point than the latter. In addition, copolymer produced with nanosized catalyst contained more 1-octene than that produced with microsized catalyst.

Metal Phosphate-Supported Pt Catalysts for CO Oxidation

Directory of Open Access Journals (Sweden)

Xiaoshuang Qian

2014-12-01

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

Study of the catalytic activity of supported technetium catalysts

International Nuclear Information System (INIS)

Spitsyn, V.I.; Mikhailenko, I.E.; Pokorovskaya, O.V.

1985-01-01

The radioactive d metal 43 Tc 99 has catalytic properties in the synthesis of ammonia. For the purpose of reducing the quantity of the radioactive metal and of increasing the specific surface, the active component was applied to BaTiO 3 and gamma-Al 2 O 3 supports. This paper uses charcoal as a support and a table presents the catalytic activity of the samples during the synthesis of ammonia. X-ray diffractometric investigation of the catalysts was carried out with the use of Cu K /SUB alpha/ radiation. It is shown that the catalysts. The values of the specific rate constants of technetium in the catalysts. The values of the specific rate constants remain practically constant for all the catalyst samples studied, attesting to the absence of a specific metal-support interaction during the synthesis of ammonia

Sulfur tolerant zeolite supported platinum catalysts for aromatics hydrogenation

Energy Technology Data Exchange (ETDEWEB)

Bergem, Haakon

1997-12-31

The increased demand for transportation fuels at the expence of heavier fuel oil has forced the refinery industry to expand their conversion capacity with hydrotreating as one of the key processes. A shift towards more diesel powered vehicles along with tightening fuel regulations demanding cleaner fuels has lead to increasing interest in catalytic processes for the manufacturing of such environmentally acceptable fuels. This provides the motivation for this thesis. Its main objective was to study possible catalysts active for desulfurization, hydrogenation, and ring-opening of aromatics all in the presence of sulfur. A close examination of the physical properties and kinetical behaviour of the chosen catalysts has been performed. A high pressure reactor setup was designed and built for activity measurements. Zeolite supported platinum catalysts were prepared and both the metal and acid functions were characterized utilizing various experimental techniques. Hydrogenation of toluene was used as a model reaction and the effect of sulfur adsorption on the activity and kinetic behaviour of the catalysts was investigated. The catalyst samples showed hydrogenation activities comparable to a commercial Pt/Al2O3 catalyst. There were no clear differences in the effect of the various sulfur compounds studied. Platinum supported on zeolite Y gave considerably more sulfur tolerant catalysts compared to Al2O3 as support. 155 refs., 58 figs., 36 tabs.

Preparation of self-supporting metallic foils of nickel isotopes

International Nuclear Information System (INIS)

Sugai, Isao.

1975-01-01

This is the fourth report on the practical methods of target preparation for use in low energy nuclear experiments following the previous one (INS-J-150). An electroplating method has been developed as a dependable and reproducible technique for making self-supporting metallic foils of nickel in the thickness range of 0.5 to 10 mg/cm 2 . The procedures minimized the necessary amount of material so that nickel isotopes could be processed economically. Impurity contamination of the nickel foils during the electroplating process was less than 500 ppm, and the thickness variation in each foil was less than 3% of the central thickness. (auth.)

Metal recovery from spent refinery catalysts by means of biotechnological strategies

International Nuclear Information System (INIS)

Beolchini, F.; Fonti, V.; Ferella, F.; Veglio, F.

2010-01-01

A bioleaching study aimed at recovering metals from hazardous spent hydroprocessing catalysts was carried out. The exhaust catalyst was rich in nickel (4.5 mg/g), vanadium (9.4 mg/g) and molybdenum (4.4 mg/g). Involved microorganisms were iron/sulphur oxidizing bacteria. Investigated factors were elemental sulphur addition, ferrous iron addition and actions contrasting a possible metal toxicity (either adding powdered activated charcoal or simulating a cross current process by means of periodical filtration). Ferrous iron resulted to be essential for metal extraction: nickel and vanadium extraction yields were 83% and 90%, respectively, while about 50% with no iron. The observed values for molybdenum extraction yields were not as high as Ni and V ones (the highest values were around 30-40%). The investigated actions aimed at contrasting a possible metal toxicity resulted not to be effective; in contrast, sequential filtration of the liquor leach had a significant negative effect on metals extraction. Nickel and vanadium dissolution kinetics resulted to be significantly faster than molybdenum dissolution ones. Furthermore, a simple first order kinetic model was successfully fitted to experimental data. All the observed results supported the important role of the indirect mechanism in bioleaching of LC-Finer catalysts.

Metal recovery from spent refinery catalysts by means of biotechnological strategies

Energy Technology Data Exchange (ETDEWEB)

Beolchini, F., E-mail: f.beolchini@univpm.it [Department of Marine Sciences, Polytechnic University of Marche, Via Brecce Bianche, 60131 Ancona (Italy); Fonti, V. [Department of Marine Sciences, Polytechnic University of Marche, Via Brecce Bianche, 60131 Ancona (Italy); Ferella, F.; Veglio, F. [Department of Chemistry, Chemical Engineering and Materials, University of L' Aquila, Monteluco di Roio, 67040 L' Aquila (Italy)

2010-06-15

A bioleaching study aimed at recovering metals from hazardous spent hydroprocessing catalysts was carried out. The exhaust catalyst was rich in nickel (4.5 mg/g), vanadium (9.4 mg/g) and molybdenum (4.4 mg/g). Involved microorganisms were iron/sulphur oxidizing bacteria. Investigated factors were elemental sulphur addition, ferrous iron addition and actions contrasting a possible metal toxicity (either adding powdered activated charcoal or simulating a cross current process by means of periodical filtration). Ferrous iron resulted to be essential for metal extraction: nickel and vanadium extraction yields were 83% and 90%, respectively, while about 50% with no iron. The observed values for molybdenum extraction yields were not as high as Ni and V ones (the highest values were around 30-40%). The investigated actions aimed at contrasting a possible metal toxicity resulted not to be effective; in contrast, sequential filtration of the liquor leach had a significant negative effect on metals extraction. Nickel and vanadium dissolution kinetics resulted to be significantly faster than molybdenum dissolution ones. Furthermore, a simple first order kinetic model was successfully fitted to experimental data. All the observed results supported the important role of the indirect mechanism in bioleaching of LC-Finer catalysts.

Montmorillonite Supported Titanium/Antimony Catalyst:Preparation, Characterization and Immobilization

Institute of Scientific and Technical Information of China (English)

CHEN Guiyong; WANG Xiaoqun; ZHAO Chuan; DU Shanyi

2014-01-01

Montmorillonite supported titanium (Ti-MMT) or antimony catalyst (Sb-MMT) has been a hot area of research on preparing polyethylene terephthalate/montmorillonite (PET/MMT) nanocomposites by in situ polymerization. So removal of Ti or Sb from Ti-MMT or Sb-MMT is not expected during in situ polymerization. Studies on immobilization of Ti or Sb on Ti-MMT or Sb-MMT are seldom reported. In this work, a series of montmorillonite supported catalysts of titanium (Ti-MMT) or antimony (Sb-MMT) and co-intercalated montmorillonite of titanium and antimony (Ti/Sb-MMT) were prepared by (1) the reaction of sodium bentonite suspension with intercalating solution containing titanium tetrachloride and/or antimony chloride, and (2) drying or calcinating the products at different temperature (100, 150, 240, 350 and 450℃). The physicochemical properties of these MMT supported catalysts were studied by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma optical emission spectrometer (ICPOES), N2 adsorption/desorption isotherms, UV-visible diffuse reflectance spectroscopy(UV-vis) and transmission electron microscopy (TEM). The immobile character of Ti or Sb on MMT supported catalysts was evaluated by a two-step method in deionized water or ethylene glycol. Several results were obtained, i e, (a) during the preparation, with an increase in drying or calcinating temperature, the amount of titanium and/or antimony species remained on these MMT supported catalysts decreased, (b) the experiments about immobile character of Ti or/and Sb showed that with an increase in drying or calcinating temperature, the immobilization of Ti and/or Sb species remained on these MMT supported catalysts increased gradually, (c) Ti-MMT calcinated at 450℃had the biggest pore volume, which means Ti-MMT had the best adsorption application prospect.

Sulphur poisoning of palladium catalysts used for methane combustion: Effect of the support

International Nuclear Information System (INIS)

Escandon, Lara S.; Ordonez, Salvador; Vega, Aurelio; Diez, Fernando V.

2008-01-01

Four different supported palladium catalysts (using alumina, silica, zirconia and titania as supports), prepared by incipient wetness impregnation, were tested as catalysts for methane oxidation in presence of sulphur dioxide. The catalyst supported on zirconia showed the best performance, whereas the silica-supported one showed the fastest deactivation. Temperature-programmed desorption experiments of the poisoned catalysts suggest that SO 2 adsorption capacity of the support plays a key role in the catalyst poisoning. In order to study the effect of promoters, expected to improve the thermal stability and thioresistance of the catalyst, commercial zirconia modified by yttrium and lantane was tested as supports. It was found that the presence of these promoters does not improve the performance of the zirconia-supported catalyst. A deactivation model - considering two different active sites (fresh and poisoning), pseudo-first order dependence on methane concentration and poisoning rate depending on sulphur concentration and fraction of non-poisoned palladium - was used for modelling the deactivation behaviour

[In situ diffuse reflectance FTIR spectroscopy study of CO adsorption on Ni2P/mesoporous molecule sieve catalysts].

Science.gov (United States)

Liu, Qian-qian; Ji, Sheng-fu; Wu, Ping-yi; Hu, Lin-hua; Huang, Xiao-fan; Zhu, Ji-qin; Li, Cheng-yue

2009-05-01

Abstract The supported nickel phosphate precursors were prepared by incipient wetness impregnation using nickel nitrate as nickel source, diammonium hydrogen phosphate as phosphorus source, and MCM-41, MCM-48, SBA-15 and SBA-16 as supports, respectively. Then, the supported Ni2 P catalysts were prepared by temperature-programmed reduction in flowing Hz from their nickel phosphate precursors. The in situ diffuse reflectance FTIR spectroscopy (DRIFTS) analysis with the probe molecule CO was carried out to characterize the surface properties. The results indicated that there were significant differences in the spectral features of the samples. The upsilon(CO) absorbances observed for adsorbed CO on mesoporous molecule sieve was attributed to weak physical adsorption. There are four different kinds of upsilon(CO) absorbances observed for adsorbed CO on Ni2 P/MCM-41 catalyst with the following assignments: (1) the formation of Ni(CO)4 at 2055 cm(-1). (2) CO terminally bonded to cus Ni(delta+) (0catalysts. The absorbance observed at 2051-2055 cm(-1) for CO adsorption on Ni2P/MCM-48, Ni2P/SBA-15 and Ni2P/SBA-16 catalysts is due to the formation of Ni(CO)4 species. The other upsilon absorbances observed at 2093-2096 cm(-1) was attributed to CO terminally bonded to cus Ni(delta+) (0

Dearomatization of jet fuel on irradiated platinum-supported catalyst

International Nuclear Information System (INIS)

Mucka, V.; Ostrihonova, A.; Kopernicky, I.; Mikula, O.

1983-01-01

The effect of ionizing radiation ( 60 Co #betta#-rays) on Pt-supported catalyst used for the dearomatization of jet fuel with distillation in the range 395 to 534 K has been studied. Pre-irradiation of the catalyst with doses in the range 10 2 to 5 x 10 4 Gy leads to the partial catalyst activation. Irradiation of the catalyst enhances its resistance to catalyst poisons, particularly to sulphur-compounds, and this is probably the reason for its catalytic activity being approx. 60 to 100% greater than that of un-irradiated catalyst. Optimum conditions for dearomatization on the irradiated catalyst were found and, by means of a rotary three-factorial experiment, it was shown that these lie at lower temperatures and lower pressures than those for un-irradiated catalyst. (author)

Dissolution of Metal Supported Spent Auto Catalysts in Acids

Directory of Open Access Journals (Sweden)

Fornalczyk A.

2016-03-01

Full Text Available Metal supported auto catalysts, have been used in sports and racing cars initially, but nowadays their application systematically increases. In Metal Substrate (supported Converters (MSC, catalytic functions are performed by the Platinum Group Metals (PGM: Pt, Pd, Rh, similarly to the catalysts on ceramic carriers. The contents of these metals make that spent catalytic converters are valuable source of precious metals. All over the world there are many methods for the metals recovery from the ceramic carriers, however, the issue of platinum recovery from metal supported catalysts has not been studied sufficiently yet. The paper presents preliminary results of dissolution of spent automotive catalyst on a metal carrier by means of acids: H2SO4, HCl, HNO3, H3PO4. The main assumption of the research was the dissolution of base metals (Fe, Cr, Al from metallic carrier of catalyst, avoiding dissolution of PGMs. Dissolution was the most effective when concentrated hydrochloric acid, and 2M sulfuric acid (VI was used. It was observed that the dust, remaining after leaching, contained platinum in the level of 0.8% and 0.7%, respectively.

Glycerol valorization: dehydration to acrolein over silica-supported niobia catalysts

NARCIS (Netherlands)

Shiju, N.R.; Brown, D.R.; Wilson, K.; Rothenberg, G.

2010-01-01

The catalytic dehydration of glycerol to acrolein is investigated over silica-supported niobia catalysts in a continuous fixed-bed gas-phase reactor. Various supported niobia catalysts are prepared and characterized using surface analysis and spectroscopic methods (XRD, UV-Vis, XPS, N2 adsorption),

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.)

Graphene: a promising two-dimensional support for heterogeneous catalysts

Directory of Open Access Journals (Sweden)

Xiaobin eFan

2015-01-01

Full Text Available Graphene has many advantages that make it an attractive two-dimensional (2D support for heterogeneous catalysts. It not only allows the high loading of targeted catalytic species, but also facilitates the mass transfer during the reaction processes. These advantages, along with its unique physical and chemical properties, endow graphene great potential as catalyst support in heterogeneous catalysis.

Wafer scale integration of catalyst dots into nonplanar microsystems

DEFF Research Database (Denmark)

Gjerde, Kjetil; Kjelstrup-Hansen, Jakob; Gammelgaard, Lauge

2007-01-01

In order to successfully integrate bottom-up fabricated nanostructures such as carbon nanotubes or silicon, germanium, or III-V nanowires into microelectromechanical systems on a wafer scale, reliable ways of integrating catalyst dots are needed. Here, four methods for integrating sub-100-nm...... diameter nickel catalyst dots on a wafer scale are presented and compared. Three of the methods are based on a p-Si layer utilized as an in situ mask, an encapsulating layer, and a sacrificial window mask, respectively. All methods enable precise positioning of nickel catalyst dots at the end...

EXAFS characterization of supported metal catalysts in chemically dynamic environments

International Nuclear Information System (INIS)

Robota, H.J.

1991-01-01

Characterization of catalysts focuses on the identification of an active site responsible for accelerating desirable chemical reactions. The identification, characterization, and selective modification of such sites is fundamental to the development of structure-function relationships. Unfortunately, this goal is far from realized in nearly all catalysts, and particularly in catalysts comprised of small supported metal particles. X-ray absorption spectroscopy (XAS) has had a dramatic effect on our understanding of supported metal particles in their resting state. However, the performance of a catalyst can not be assessed from such simple resting state measurements. Among the factors which influence catalyst performance are the exact catalyst composition, including the support and any modifiers; particle size; catalyst finishing and pretreatment conditions; pressure, composition, and temperature of the operating environment; time. Gaining an understanding of how the structure of a catalytic site can change with such an array of variables requires that we begin to develop measurement methods which are effective under chemically dynamic conditions. Ideally, it should be possible to obtain a full X-ray absorption spectrum of each element thought to have a causal relationship with observed catalyst properties. From these spectra, we can optimally extract only a relatively limited amount of information which we must then piece together with information derived from other characterization methods and intuition to arrive at a hypothetical structure of the operating catalyst. Information about crystallinity, homogeneity, and general disorder can be obtained from the Debye-Waller factor. Finally, through analogy with known compounds, the electronic structure of the active atoms can be inferred from near edge absorption features

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

Dry Reforming of Methane Using a Nickel Membrane Reactor

Directory of Open Access Journals (Sweden)

Jonas M. Leimert

2017-12-01

Full Text Available Dry reforming is a very interesting process for synthesis gas generation from CH 4 and CO 2 but suffers from low hydrogen yields due to the reverse water–gas shift reaction (WGS. For this reason, membranes are often used for hydrogen separation, which in turn leads to coke formation at the process temperatures suitable for the membranes. To avoid these problems, this work shows the possibility of using nickel self-supported membranes for hydrogen separation at a temperature of 800 ∘ C. The higher temperature effectively suppresses coke formation. The paper features the analysis of the dry reforming reaction in a nickel membrane reactor without additional catalyst. The measurement campaign targeted coke formation and conversion of the methane feedstock. The nickel approximately 50% without hydrogen separation. The hydrogen removal led to an increase in methane conversion to 60–90%.

Practical, economical, and eco-friendly starch-supported palladium catalyst for Suzuki coupling reactions.

Science.gov (United States)

Baran, Talat

2017-06-15

In catalytic systems, the support materials need to be both eco friendly and low cost as well as having high thermal and chemical stability. In this paper, a novel starch supported palladium catalyst, which had these outstanding properties, was designed and its catalytic activity was evaluated in a Suzuki coupling reaction under microwave heating with solvent-free and mild reaction conditions. The starch supported catalyst gave remarkable reaction yields after only 5min as a result of the coupling reaction of the phenyl boronic acid with 23 different substrates, which are bearing aril bromide, iodide, and chloride. The longevity of the catalyst was also investigated, and the catalyst could be reused for 10 runs. The starch supported Pd(II) catalyst yielded remarkable TON (up to 25,000) and TOF (up to 312,500) values by using a simple, fast and eco-friendly method. In addition, the catalytic performance of the catalyst was tested against different commercial palladium catalysts, and the green starch supported catalyst had excellent selectivity. The catalytic tests showed that the novel starch based palladium catalyst proved to be an economical and practical catalyst for the synthesis of biaryl compounds. Copyright © 2017 Elsevier Inc. All rights reserved.

Nickel Dermatitis - Nickel Excretion

DEFF Research Database (Denmark)

Menné, T.; Thorboe, A.

1976-01-01

Nickel excretion in urine in four females -sensitive to nickel with an intermittent dyshidrotic eruption was measured with flameless atomic absorption. Excretion of nickel was found to be increased in association with outbreaks of vesicles. The results support the idea that the chronic condition ...

Development and characterization of nickel catalysts supported in CeO{sub 2}-ZrO{sub 2}-Al{sub 2}O{sub 3}, CeO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} e ZrO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} matrixes evaluated for methane reforming reactions; Desenvolvimento e caracterização de catalisadores de níquel suportados em matrizes CeO{sub 2}-ZrO{sub 2}-Al{sub 2}O{sub 3}, CeO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} e ZrO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} avaliados para as reações de reforma do metano

Energy Technology Data Exchange (ETDEWEB)

Abreu, Amanda Jordão de

2012-07-01

Nowadays, the methane reforming is large interest industrial for the take advantage of these gas in production the hydrogen and synthesis gas (syngas). Among in the reactions of methane stand of the reactions steam reforming and carbon dioxide reforming of methane. The main catalysts uses in the methane reforming is Ni/Al{sub 2}O{sub 3}. However, the supported-nickel catalyst is susceptible to the deactivation or the destruction by coke deposition. The carbon dissolves in the nickel crystallite and its diffuses through the nickel, leading for formation of the carbon whiskers, which results in fragmentation of the catalyst. Modification of such catalysts, like incorporation of suitable promoters, is desirable to achieve reduction of the methane hydrogenolysis and/or promotion of the carbon gasification. Catalysts 5%Ni/Al{sub 2}O{sub 3} supported on solid solutions formed by ZrO{sub 2}-CeO{sub 2}, La{sub 2}O{sub 3} and CeO{sub 2}-ZrO{sub 2}-La{sub 2}O{sub 3} were prepared, characterized and evaluated in reactions steam and carbon dioxide reforming and partial oxidation of methane with objective the value effect loading solution solid in support. The supports were prepared by co-precipitation method and catalysts were prepared by impregnation method and calcined at 500 deg C. The supports and catalysts were characterized by Nitrogen Adsorption, method -rays diffraction (XRD), X-rays dispersive spectroscopy (XDS), spectroscopy in the region of the ultraviolet and the visible (UV-vis NIR) to and temperature programmed reduction (TPR), Raman Spectroscopy, X-ray absorption spectroscopy and Thermogravimetric Analysis. After all the catalytic reactions check which the addition of solid solution is beneficial for Ni/Al{sub 2}O{sub 3} catalysts and the best catalysts are Ni/CeO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3}. (author)

Production of Renewable Hydrogen from Glycerol Steam Reforming over Bimetallic Ni-(Cu,Co,Cr Catalysts Supported on SBA-15 Silica

Directory of Open Access Journals (Sweden)

Alicia Carrero

2017-02-01

Full Text Available Glycerol steam reforming (GSR is a promising alternative to obtain renewable hydrogen and help the economics of the biodiesel industry. Nickel-based catalysts are typically used in reforming reactions. However, the choice of the catalyst greatly influences the process, so the development of bimetallic catalysts is a research topic of relevant interest. In this work, the effect of adding Cu, Co, and Cr to the formulation of Ni/SBA-15 catalysts for hydrogen production by GSR has been studied, looking for an enhancement of its catalytic performance. Bimetallic Ni-M/SBA-15 (M: Co, Cu, Cr samples were prepared by incipient wetness co-impregnation to reach 15 wt % of Ni and 4 wt % of the second metal. Catalysts were characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES, N2-physisorption, X-ray powder diffraction (XRD, hydrogen temperature programmed reduction (H2-TPR, transmission electron microscopy (TEM, scanning electron microscopy (SEM, and thermogravimetric analyses (TGA, and tested in GSR at 600 °C and atmospheric pressure. The addition of Cu, Co, and Cr to the Ni/SBA-15 catalyst helped to form smaller crystallites of the Ni phase, this effect being more pronounced in the case of the Ni-Cr/SBA-15 sample. This catalyst also showed a reduction profile shifted towards higher temperatures, indicating stronger metal-support interaction. As a consequence, the Ni-Cr/SBA-15 catalyst exhibited the best performance in GSR in terms of glycerol conversion and hydrogen production. Additionally, Ni-Cr/SBA-15 achieved a drastic reduction in coke formation compared to the Ni/SBA-15 material.

Dispersion of nano-nickel into γ-Al2O3 studied by positron

International Nuclear Information System (INIS)

Jun Zhu; Wang, S.J.; Luo, X.H.

2003-01-01

The positron annihilation lifetime spectra were measured as a function of the content of the nano-nickel, of temperature, as well as of the heating time for the supported nano-nickel catalyst that was prepared by mechanical mixture nano-metal nickel particles with gamma-alumina (γ-Al 2 O 3 ). The lifetime spectra were well resolved into four lifetime components. The longest lifetime τ 4 was assigned to ortho-positronium annihilating in the secondary pore of the γ-Al 2 O 3 . The results showed that part of the nano-nickel had entered into γ-Al 2 O 3 by thermal diffusion at heating above 200 deg. C and had interacted with the face of the γ-Al 2 O 3 , but the length of diffusion is not very large

Dispersion of nano-nickel into γ-Al 2O 3 studied by positron

Science.gov (United States)

Jun, Zhu; Wang, S. J.; Luo, X. H.

2003-10-01

The positron annihilation lifetime spectra were measured as a function of the content of the nano-nickel, of temperature, as well as of the heating time for the supported nano-nickel catalyst that was prepared by mechanical mixture nano-metal nickel particles with gamma-alumina ( γ-Al 2O 3). The lifetime spectra were well resolved into four lifetime components. The longest lifetime τ4 was assigned to ortho-positronium annihilating in the secondary pore of the γ-Al 2O 3. The results showed that part of the nano-nickel had entered into γ-Al 2O 3 by thermal diffusion at heating above 200°C and had interacted with the face of the γ-Al 2O 3, but the length of diffusion is not very large.

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

Templating Routes to Supported Oxide Catalysts by Design

Energy Technology Data Exchange (ETDEWEB)

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

2016-09-08

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

{alpha}-Al{sub 2}O{sub 3} catalyst supports for synthesis gas production: influence of different alumina bonding agents on support and catalyst properties

Energy Technology Data Exchange (ETDEWEB)

Marturano, M. [Centro de Investigacion y Desarrollo en Procesos Cataliticos, La Plata (Argentina); Aglietti, E.F. [Centro de Tecnologia de Recursos Minerales y Ceramica (CETMIC), Gonnet (Argentina); Ferretti, O. [Centro de Investigacion y Desarrollo en Procesos Cataliticos, La Plata (Argentina)]|[Univ. Nacional de La Plata, Dept. de Ingenieria Quimica de la Facultad de Ingenieria, La Plata (Argentina)

1997-02-01

Aluminas are widely used as catalytic supports in chemical reactions. Reforming reactions to obtain synthesis gas requires good mechanical strength and low sintering behaviour. In this work, the influence of bentonite, aluminium phosphate and alumina gel as binder agents of a calcined {alpha}-Al{sub 2}O{sub 3} are analyzed with respect to support and catalytic properties. The {alpha}-Al{sub 2}O{sub 3} supports, calcined at 1300 C, are then impregnated with solutions of Ni and Al inorganic salts to obtain the catalysts and are finally tested in the reforming reaction of methane to synthesis gas at 500-900 C. Supports and catalysts are characterized by XRD, SEM, N{sub 2} adsorption, mechanical strength test and other techniques. Mechanical strength depends on the type and quantity of binder material used during support preparation. The influence of the support on the performance of the resulting catalyst is evidenced by means of catalytic tests. (orig.) 8 refs.

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

Electroreduction of oxygen on carbon-supported gold catalysts

International Nuclear Information System (INIS)

Erikson, Heiki; Juermann, Gea; Sarapuu, Ave; Potter, Robert J.; Tammeveski, Kaido

2009-01-01

The electrochemical reduction of oxygen was studied on Au/C catalysts (20 and 30 wt%) in 0.5 M H 2 SO 4 and 0.1 M KOH solutions using the rotating disk electrode (RDE) method. The thickness of the Au/C-Nafion layers was varied between 1.5 and 10 μm. The specific activity of Au was independent of catalyst loading in both solutions, indicating that the transport of reactants through the catalyst layer does not limit the process of oxygen reduction under these conditions. The mass activity of 20 wt% Au/C catalysts was higher due to smaller particle size. The number of electrons involved in the reaction and the Tafel slopes were found; the values of these parameters are similar to that of bulk polycrystalline gold and indicate that the mechanism of O 2 reduction is not affected by carbon support or the catalyst configuration.

Catalysts for the production of hydrocarbons from carbon monoxide and water

Science.gov (United States)

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

1985-11-06

A method of converting low H/sub 2//CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200 to 350/sup 0/C in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinum, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n + 1) greater than or equal to x greater than or equal to O and for olefinic hydrocarbons: 2n greater than or equal to x greater than or equal to O where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

Catalyst for reforming hydrocarbons with water vapors

International Nuclear Information System (INIS)

Nicklin, T.; Farrington, F.; Whittaker, J.R.

1979-01-01

The catalyst should reform hydrocarbons with water vapour. It consists of a carrier substance (preferably clay) on whose surface the catalytically active substances are formed. By impregnation one obtains this with a mixture of thermally destructable nickel and uranium compounds and calcination of the impregnated carrier. The catalyst is marked by a definite weight ratio of uranium to nickel (about 0.6 to 1), the addition of barium compounds and a maximum limit of these additives. All details of manufacture and the range of variations are described in detail. (UWI) [de

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

Wire gauze and cordierite supported noble metal catalysts for passive autocatalytic recombiner

International Nuclear Information System (INIS)

Sanap, Kiran K.; Varma, S.; Waghmode, S.B.; Bharadwaj, S.R.

2015-01-01

Highlights: • Synthesis by electroless deposition method and chemical reduction route. • Particle size of 0.1–0.5 μm & 3.5–5 nm for Pt–Pd/Wg & Pt–Pd/Cord catalysts. • Active for H_2 and O_2 reaction with initial H_2 concentration of 1.5 to 7% in air. • Active in presence of different contaminants like CO_2, CH_4, CO & relative humidity. • Enhanced resistance of Pt–Pd/Cord catalyst towards the poisoning of CO. - Abstract: Hydrogen released in nuclear reactor containment under severe accident scenario poses a threat to containment and hence needs to be regulated by catalytic recombination. Mixed noble metal catalysts with platinum–palladium supported on stainless steel wire gauze and cordierite support have been developed for this purpose. The developed catalysts have been found to be highly efficient for removal of hydrogen concentration in the range of 1.5 to 7.0% v/v in air. Though both the catalysts exhibit similar kinetics for lower hydrogen concentration, cordierite supported catalysts exhibits better kinetic rate at higher hydrogen concentration. The performances of these catalysts in presence of various probable catalytic poison like carbon monoxide and catalytic inhibitors like moisture, carbon dioxide, and hydrocarbons provide data for use of these catalysts under the actual scenario. Compared to stainless steel wire gauze supported catalyst, the cordierite based catalyst are found to exhibit enhanced resistance towards carbon monoxide and limited temperature rise for safer application at higher hydrogen concentrations.

Fuel cell testing of Pt–Ru catalysts supported on differently prepared and pretreated carbon nanotubes

International Nuclear Information System (INIS)

Tokarz, Wojciech; Lota, Grzegorz; Frackowiak, Elzbieta; Czerwiński, Andrzej; Piela, Piotr

2013-01-01

Proton-exchange membrane fuel cell (PEMFC) testing of Pt–Ru catalysts supported on differently prepared multiwall carbon nanotube (MCNT) supports was performed to elucidate the influence of the different supports on the operating characteristics of the catalysts under real direct methanol fuel cell (DMFC) anode and H 2 -PEMFC anode conditions. The MCNTs were either thin, entangled or thick, disentangled. Pretreatment of the MCNTs was also done and it was either high-temperature KOH etching or annealing (graphitization). The performance of the catalysts was compared against the performance of a commercial Pt–Ru catalyst supported on a high-surface-area carbon black. Among the different MCNT supports, the graphitized, entangled support offered the best performance in all tests, which was equal to the performance of the commercial catalyst, despite the MCNT catalyst layer was ca. 2.2 times thicker than the carbon black catalyst layer. Even for an MCNT catalyst layer, which was almost 7 times thicker than the carbon black catalyst layer, the transport limitations were not prohibitive. This confirmed the expected potential of nanotube supports for providing superior reactant transport properties of the PEMFC catalyst layers

Palladium catalysts deposited on silica materials: Comparison of catalysts based on mesoporous and amorphous supports in Heck reaction

Czech Academy of Sciences Publication Activity Database

Demel, J.; Čejka, Jiří; Štěpnička, P.

2010-01-01

Roč. 329, 1-2 (2010), s. 13-20 ISSN 1381-1169 R&D Projects: GA ČR GA104/09/0561 Institutional research plan: CEZ:AV0Z40400503 Keywords : heterogeneous catalysts * immobolized catalysts * supported catalysts Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.872, year: 2010

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.

Carbon a support for sulfide catalysts

NARCIS (Netherlands)

Vissers, J.P.R.; Lensing, T.J.; Mercx, F.P.M.; Beer, de V.H.J.; Prins, R.

1983-01-01

Two types of carbon materials, carbon black composite and carbon covered alumina, were studied for-their use as support for sulfide catalysts. The following parameters were varied: type of carbon black, carbon coverage of the alumina and carbon pretreatment. Pore size distributions were determined

Silica-supported Preyssler Nanoparticles as New Catalysts in the ...

African Journals Online (AJOL)

A new and efficient method for the preparation of 4(3H)-quinazolinones from the condensation of anthranilic acid, orthoester and substituted anilines, in the presence of catalytic amounts of silica-supported Preyssler nanoparticles is reported. The catalyst performs very well in comparison with other catalysts reported before.

Ultrasmall Dispersible Crystalline Nickel Oxide Nanoparticles as High-Performance Catalysts for Electrochemical Water Splitting

Czech Academy of Sciences Publication Activity Database

Fominykh, K.; Feckl, J. M.; Sicklinger, J.; Döblinger, M.; Böcklein, S.; Ziegler, J.; Peter, L.; Rathouský, Jiří; Scheidt, E.-W.; Bein, T.; Fattakhova-Rohlfing, D.

2014-01-01

Roč. 24, č. 21 (2014), s. 3123-3129 ISSN 1616-301X Institutional support: RVO:61388955 Keywords : electrocatalysis * nickel oxide * nanocrystals Subject RIV: CG - Electrochemistry Impact factor: 11.805, year: 2014

High-Throughput Screening of Heterogeneous Catalysts for the Conversion of Furfural to Bio-Based Fuel Components

Directory of Open Access Journals (Sweden)

Roberto Pizzi

2015-12-01

Full Text Available The one-pot catalytic reductive etherification of furfural to 2-methoxymethylfuran (furfuryl methyl ether, FME, a valuable bio-based chemical or fuel, is reported. A large number of commercially available hydrogenation heterogeneous catalysts based on nickel, copper, cobalt, iridium, palladium and platinum catalysts on various support were evaluated by a high-throughput screening approach. The reaction was carried out in liquid phase with a 10% w/w furfural in methanol solution at 50 bar of hydrogen. Among all the samples tested, carbon-supported noble metal catalysts were found to be the most promising in terms of productivity and selectivity. In particular, palladium on charcoal catalysts show high selectivity (up to 77% to FME. Significant amounts of furfuryl alcohol (FA and 2-methylfuran (2-MF are observed as the major by-products.

Graphitized Carbon: A Promising Stable Cathode Catalyst Support Material for Long Term PEMFC Applications.

Science.gov (United States)

Mohanta, Paritosh Kumar; Regnet, Fabian; Jörissen, Ludwig

2018-05-28

Stability of cathode catalyst support material is one of the big challenges of polymer electrolyte membrane fuel cells (PEMFC) for long term applications. Traditional carbon black (CB) supports are not stable enough to prevent oxidation to CO₂ under fuel cell operating conditions. The feasibility of a graphitized carbon (GC) as a cathode catalyst support for low temperature PEMFC is investigated herein. GC and CB supported Pt electrocatalysts were prepared via an already developed polyol process. The physical characterization of the prepared catalysts was performed using transmission electron microscope (TEM), X-ray Powder Diffraction (XRD) and inductively coupled plasma optical emission spectrometry (ICP-OES) analysis, and their electrochemical characterizations were conducted via cyclic voltammetry(CV), rotating disk electrode (RDE) and potential cycling, and eventually, the catalysts were processed using membrane electrode assemblies (MEA) for single cell performance tests. Electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SEM) have been used as MEA diagonostic tools. GC showed superior stability over CB in acid electrolyte under potential conditions. Single cell MEA performance of the GC-supported catalyst is comparable with the CB-supported catalyst. A correlation of MEA performance of the supported catalysts of different Brunauer⁻Emmett⁻Teller (BET) surface areas with the ionomer content was also established. GC was identified as a promising candidate for catalyst support in terms of both of the stability and the performance of fuel cell.

Catalyst in Basic Oleochemicals

Directory of Open Access Journals (Sweden)

Eva Suyenty

2007-10-01

Full Text Available Currently Indonesia is the world largest palm oil producer with production volume reaching 16 million tones per annum. The high crude oil and ethylene prices in the last 3 – 4 years contribute to the healthy demand growth for basic oleochemicals: fatty acids and fatty alcohols. Oleochemicals are starting to replace crude oil derived products in various applications. As widely practiced in petrochemical industry, catalyst plays a very important role in the production of basic oleochemicals. Catalytic reactions are abound in the production of oleochemicals: Nickel based catalysts are used in the hydrogenation of unsaturated fatty acids; sodium methylate catalyst in the transesterification of triglycerides; sulfonic based polystyrene resin catalyst in esterification of fatty acids; and copper chromite/copper zinc catalyst in the high pressure hydrogenation of methyl esters or fatty acids to produce fatty alcohols. To maintain long catalyst life, it is crucial to ensure the absence of catalyst poisons and inhibitors in the feed. The preparation methods of nickel and copper chromite catalysts are as follows: precipitation, filtration, drying, and calcinations. Sodium methylate is derived from direct reaction of sodium metal and methanol under inert gas. The sulfonic based polystyrene resin is derived from sulfonation of polystyrene crosslinked with di-vinyl-benzene. © 2007 BCREC UNDIP. All rights reserved.[Presented at Symposium and Congress of MKICS 2007, 18-19 April 2007, Semarang, Indonesia][How to Cite: E. Suyenty, H. Sentosa, M. Agustine, S. Anwar, A. Lie, E. Sutanto. (2007. Catalyst in Basic Oleochemicals. Bulletin of Chemical Reaction Engineering and Catalysis, 2 (2-3: 22-31.  doi:10.9767/bcrec.2.2-3.6.22-31][How to Link/DOI: http://dx.doi.org/10.9767/bcrec.2.2-3.6.22-31 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/6

Nanostructured Co3O4 grown on nickel foam: An efficient and readily recyclable 3D catalyst for heterogeneous peroxymonosulfate activation.

Science.gov (United States)

Yuan, Ruixia; Hu, Lin; Yu, Peng; Wang, Huaiyuan; Wang, Zhaohui; Fang, Jingyun

2018-05-01

Cobalt-based heterogeneous catalyst has been recognized as one of most efficient activators for peroxymonosulfate (PMS) decomposition, but usually suffers from the poor stability and difficulty to recover and reuse. Here easily recyclable cobalt oxide (Co 3 O 4 ) nanowires and nanoflowers grown on nickel foam (NF) are fabricated by a hydrothermal and calcination method. The prepared 3D Co 3 O 4 /NF catalyst is characterized and applied as a heterogeneous catalyst for PMS activation to generate sulfate radicals for decomposition of Acid Orange 7 (AO7). The results show that the AO7 degradation rate increases with cobalt loading and PMS dosage, but decreases with the increase of solution pH. The Co 3 O 4 /NF catalyst using 2 mM Co(NO 3 ) 2 ·6H 2 O as cobalt source exhibits highest activity, and almost complete decolorization could be achieved within 30 min. The diverse effects of coexisting anions (SO 4 2- , HCO 3 - , NO 3 - and Cl - ) on AO7 degradation are observed and explained. After 10 consecutive runs, excellent catalytic reactivity of the catalyst remains while the level of leached cobalt during the catalyst usage is much lower than the maximum allowable concentration in drinking and natural water. More importantly, the macroscopic Co 3 O 4 /NF catalyst shows advantage of easy recycling after application compared to traditional catalysts. It is believed that the as-prepared Co 3 O 4 /NF is promising to be an effective and green heterogeneous catalyst for PMS activation to degrade organic pollutants for environmental application. Copyright © 2018 Elsevier Ltd. All rights reserved.

Attrition resistant gamma-alumina catalyst support

Science.gov (United States)

Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

2006-03-14

A .gamma.-alumina catalyst support having improved attrition resistance produced by a method comprising the steps of treating a particulate .gamma.-alumina material with an acidic aqueous solution comprising water and nitric acid and then, prior to adding any catalytic material thereto, calcining the treated .gamma.-alumina.

Graphene supported heterogeneous catalysts for Li–O{sub 2} batteries

Energy Technology Data Exchange (ETDEWEB)

Alaf, M., E-mail: mirac.alaf@bilecik.edu.tr [Bilecik Seyh Edebali University, Engineering Faculty, Department of Metallurgy and Materials Engineering, Gulumbe Campus, Bilecik 11210 (Turkey); Tocoglu, U.; Kartal, M.; Akbulut, H. [Sakarya University, Engineering Faculty, Department of Metallurgy and Materials Engineering, Esentepe Campus, Sakarya 54187 (Turkey)

2016-09-01

Graphical abstract: - Highlights: • Free-standing and flexible electrodes were prepared for Li–air batteries. • α-MnO{sub 2} nanorods, Pt nanoparticles and graphene were used. • α-MnO{sub 2} and Pt catalyst improved OER/ORR kinetics. - Abstract: In this study production and characterization of free-standing and flexible (i) graphene, (ii) α-MnO{sub 2}/graphene, (iii) Pt/graphene (iv) α-MnO{sub 2}/Pt/graphene composite cathodes for Li–air batteries were reported. Graphene supported heterogeneous catalysts were produced by a facile method. In order to prevent aggregation of graphene sheets and increase not only interlayer distance but also surface area, a trace amount multi-wall carbon nano tube (MWCNT) was introduced to the composite structure. The obtained composite catalysts were characterized by SEM, X-ray diffraction, N{sub 2} adsorption–desorption analyze and Raman spectroscopy. The electrochemical characterization tests including galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS) measurement of catalyst were carried out by using an ECC-Air test cell. These highly active graphene supported heterogeneous composite catalysts provide competitive properties relative to other catalyst materials for Li–air batteries.

Design of heterogeneous catalysts

DEFF Research Database (Denmark)

Frey, Anne Mette

was inspired by a computational screening, suggesting that alloys such as Ni-Fe, Co-Ni, and Co-Fe should show superior activity to the industrially used nickel catalyst. Especially the Ni-Fe system was considered to be interesting, since such alloy catalysts should be both more active and cheaper than the Ni...... catalyst. The results from the screening were experimentally verified for CO hydrogenation, CO2 hydrogenation, and simultaneous CO and CO2 hydrogenation by bimetallic Ni-Fe catalysts. These catalysts were found to be highly active and selective. The Co-Ni and Co-Fe systems were investigated for CO...... well, and the best catalyst prepared had a C5+ yield almost a factor of two higher than a standard air calcined Co catalyst. In the NH3-SCR reaction it is desirable to develop an active and stable catalyst for NOx removal in automotive applications, since the traditionally used vanadium-based catalyst...

Template-Assisted Wet-Combustion Synthesis of Fibrous Nickel-Based Catalyst for Carbon Dioxide Methanation and Methane Steam Reforming.

Science.gov (United States)

Aghayan, M; Potemkin, D I; Rubio-Marcos, F; Uskov, S I; Snytnikov, P V; Hussainova, I

2017-12-20

Efficient capture and recycling of CO 2 enable not only prevention of global warming but also the supply of useful low-carbon fuels. The catalytic conversion of CO 2 into an organic compound is a promising recycling approach which opens new concepts and opportunities for catalytic and industrial development. Here we report about template-assisted wet-combustion synthesis of a one-dimensional nickel-based catalyst for carbon dioxide methanation and methane steam reforming. Because of a high temperature achieved in a short time during reaction and a large amount of evolved gases, the wet-combustion synthesis yields homogeneously precipitated nanoparticles of NiO with average particle size of 4 nm on alumina nanofibers covered with a NiAl 2 O 4 nanolayer. The as-synthesized core-shell structured fibers exhibit outstanding activity in steam reforming of methane and sufficient activity in carbon dioxide methanation with 100% selectivity toward methane formation. The as-synthesized catalyst shows stable operation under the reaction conditions for at least 50 h.

THE THEORY OF DEVELOPMENT OF SUPPORTED METAL-COMPLEX CATALYSTS

Directory of Open Access Journals (Sweden)

T. L. Rakitskaya

2015-06-01

Full Text Available Some results of the investigations for the purpose of development of supported metal-complex catalysts for phosphine and carbon monoxide oxidation as well as for ozone decomposition are summarized. The activity of such catalysts has been found to depend not only on a nature of a central atom and ligands but also on a nature of supports. The theoretical model explaining mechanisms of surface complex formation taking into account the influence of physicochemical and structural-adsorption properties of the supports (SiO2, Al2O3, carbon materials, zeolites, dispersed silicas, lamellar aluminosilicates, etc. has been proposed. For quantitative description of the support effect, such a thermodynamic parameter as the adsorbed water activity assignable with the help of water vapor adsorption isotherms has been introduced. Successive stability constants of the surface metal complexes have been calculated by the kinetic method and, hence, compositions and partial catalytic activity of the latter have been determined. Taking into account the competitive adsorption of metal ions on the supports, some schemes of formation of surface bimetallic complexes have been suggested. The compositions of the supported metal-complex catalysts have been optimized to meet requirements of their use in respirators and plants for air purification from foregoing gaseous toxicants.

Synthesis and characterization of platinum supported on alumina doped with cerium catalyst

International Nuclear Information System (INIS)

Yusof Abdullah; Abd Fatah Awang Mat; Mohd Ali Sufi; Sarimah Mahat; Razali Kassim; Nurhaslinda Abdullah.

1996-03-01

The synthesis and characterization of gamma-alumina doped with cerium as platinum support for the automobile exhaust catalyst are described. Platinum/alumina/ceria catalyst were prepared by impregnation of hexachloroplatinic acid and sintered at 500 degree Celsius to obtain metal dispersions of 1.0 wt%. Catalyst distribution inside the powder and the effects of the addition of cerium to alumina were analyzed by the scanning electron microscopy (SEM) and x-ray fluorescence spectroscopy (XRF). The results showed that the alumina - supported catalysts contained well dispersion of the noble metal

Development of industrial hydrogenating catalyst on rhenium base

International Nuclear Information System (INIS)

Chistyakova, G.A.; Bat', I.I.; Rebrova, V.V.

1975-01-01

Processes for forming rhenium catalysts on carbon carrier and their catalytic properties in nitrobenzene (NB) reduction were studied. Application of an ammonia preparation to the carbon surface produced impregnated carbon saturated at room temperature with a water solution of the ammonia preparation, taken in a volume equal to the volumetric capacity of the carbon. With one impregnation, 2% rhenium was taken up. Catalysts containing more than 5% rhenium were obtained by impregnating the carbon with heating and use of more concentrated solutions. Catalysts made in this way and dried at 100 0 C had the composition Re 2 OH/carbon/. The most active catalysts were those reduced at 200-250 0 C; higher temperatures, up to 300-500 0 C, decreased the activity. Study of the catalytic properties of the rhenium catalysts in a liquid phase reduction of NB showed that the specific activity of rhenium depends only slightly on the content of the active component in the catalyst and is close to the specific activity of palladium and considerably exceeds that of nickel. Study of the effect of the NB concentration and hydrogen pressure on the activity and stability of the 5% rhenium catalyst indicated that with NB concentrations from 50 to 10% the process takes place at an essentially constant rate; the order of the reaction was close to zero with an apparent activation energy of about 7000 cal/mole. At pressures of 15-200 atm the yield with the 5% catalyst was proportional to the hydrogen pressure. A big advantage of the rhenium catalysts in the reduction of NB is their high selectivity. With a higher activity than palladium and nickel catalysts, 5% rhenium catalyst produces a high operating capacity in a wide range of contact charges, which has considerable significance for industrial use in contact apparatus of the column type. Comparison of the costs of rhenium catalysts and granular carbon carrier with those of nickel, platinum, and palladium showed that 5% rhenium catalyst can

Development of Cu and Ni catalysts supported on ZrO2 for the generation of H2 by means of the reaction of reformed methanol in atmosphere oxidizer

International Nuclear Information System (INIS)

Lopez C, P.

2012-01-01

ZrO 2 was prepared by the sol-gel method and calcined at 450 C. The prepared zirconia was impregnated with an aqueous solution of Cu(CH 3 CO 2 ) 2 ·H 2 O or NiNO 3 ·6H 2 O at an appropriate concentration to yield 3 wt % of copper or nickel, respectively, in the mono metallic catalysts. Three bimetallic samples were prepared at 80% Cu and 20% Ni respectively to obtain 3 wt % of total metallic phase. Surface area of the Cu-Ni base catalysts supported on ZrO 2 oxide showed differences as a function of the metal addition. Between them, the Cu/ZrO 2 catalyst had the lowest surface area than other catalysts. X-ray diffraction patterns of the bimetallic catalysts did not show diffraction peaks of the Cu, Ni or bimetallic Cu-Ni alloys. In addition, TPR profiles of the bimetallic catalysts had the lowest reduction temperature compared with the mono metallic samples. The reactivity of the catalysts in the range of 250-350 C showed that the samples prepared by successive impregnation had the highest catalytic activity than the other catalysts studied. Also the selectivity for H 2 production was higher for these catalysts. This finding was associated to the presence of the bimetallic Cu-Ni nanoparticles, as was evidenced by Tem-EDX analysis. (Author)

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.

Synthesis and characterization of MCM-41-supported nano zirconia catalysts

Directory of Open Access Journals (Sweden)

Mohamed S. Abdel Salam

2015-03-01

Full Text Available Series of MCM-41 supported sulfated Zirconia (SZ catalysts with different loadings (2.5–7.5% wt. were prepared using direct impregnation method. The acquired solid catalysts were characterized structurally and chemically using X-RD, HRTEM, BET, FT-IR, Raman spectroscopy and TPD analysis. The acidity of the solid catalysts was investigated through cumene cracking and isopropanol dehydration at different temperatures. As the SZ loading increases, the surface acidity of the mesoporous catalysts was enhanced, this was reflected by the higher catalytic activity toward cumene cracking and isopropanol dehydration.

Preparation and characterization of bi-metallic nanoparticle catalyst having better anti-coking properties using reverse micelle technique

Science.gov (United States)

Zacharia, Thomas

Energy needs are rising on an exponential basis. The mammoth energy sources like coal, natural gas and petroleum are the cause of pollution. The large outcry for an alternate energy source which is environmentally friendly and energy efficient is heard during the past few years. This is where “Clean-Fuel” like hydrogen gained its ground. Hydrogen is mainly produced by steam methane reforming (SMR). An alternate sustainable process which can reduce the cost as well as eliminate the waste products is Tri-reforming. In both these reforming processes nickel is used as catalyst. However as the process goes on the catalyst gets deactivated due to coking on the catalytic surface. This goal of this thesis work was to develop a bi-metallic catalyst which has better anti-coking properties compared to the conventional nickel catalyst. Tin was used to dope nickel. It was found that Ni3Sn complex around a core of Ni is coking resistant compared to pure nickel catalyst. Reverse micelle synthesis of catalyst preparation was used to control the size and shape of catalytic particles. These studies will benefit researches on hydrogen production and catalyst manufactures who work on different bi-metallic combinations.

Graphitic Carbon Nitride as a Catalyst Support in Fuel Cells and Electrolyzers

International Nuclear Information System (INIS)

Mansor, Noramalina; Miller, Thomas S.; Dedigama, Ishanka; Jorge, Ana Belen; Jia, Jingjing; Brázdová, Veronika; Mattevi, Cecilia; Gibbs, Chris; Hodgson, David; Shearing, Paul R.; Howard, Christopher A.; Corà, Furio; Shaffer, Milo; Brett, Daniel J.L.

2016-01-01

Highlights: • Graphitic carbon nitride (gCN) describes many materials with different structures. • gCNs can exhibit excellent mechanical, chemical and thermal resistance. • A major obstacle for pure gCN catalyst supports is limited electronic conductivity. • Composite/Hybrid gCN structures show excellent performance as catalyst supports. • gCNs have great potential for use in fuel calls and water electrolyzers. - Abstract: Electrochemical power sources, such as polymer electrolyte membrane fuel cells (PEMFCs), require the use of precious metal catalysts which are deposited as nanoparticles onto supports in order to minimize their mass loading and therefore cost. State-of-the-art/commercial supports are based on forms of carbon black. However, carbon supports present disadvantages including corrosion in the operating fuel cell environment and loss of catalyst activity. Here we review recent work examining the potential of different varieties of graphitic carbon nitride (gCN) as catalyst supports, highlighting their likely benefits, as well as the challenges associated with their implementation. The performance of gCN and hybrid gCN-carbon materials as PEMFC electrodes is discussed, as well as their potential for use in alkaline systems and water electrolyzers. We illustrate the discussion with examples taken from our own recent studies.

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

International Nuclear Information System (INIS)

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

2000-01-01

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

Effects of adding lanthanum to Ni/ZrO2 catalysts on ethanol steam reforming

International Nuclear Information System (INIS)

Profeti, Luciene Paula Roberto; Habitzheuter, Filipe; Assaf, Elisabete Moreira

2012-01-01

The catalytic performance of Ni/ZrO 2 catalysts loaded with different lanthanum content for steam reforming of ethanol was investigated. Catalysts were characterized by BET surface area, X-ray diffraction, UV-vis spectroscopy, temperature programmed reduction, and X-ray absorption fine structure techniques. Results showed that lanthanum addition led to an increase in the degree of reduction of both NiO and nickel surface species interacting with the support, due to the higher dispersion effect. The best catalytic performance at 450 deg C was found for the Ni/12LZ catalyst, which exhibited an effluent gaseous mixture with the highest H 2 yield. (author)

Hydrogenation of carbon monoxide on WO/sub 3/-Supported ruthenium catalysts

Energy Technology Data Exchange (ETDEWEB)

Yoshinari, Tomohiro; Suganuma, Fujio; Sera, Chikara

1988-01-01

In this study, a WO/sub 3/-supported catalyst was prepared to conduct hydrogenation of CO for examining the product distribution and composition of hydrocarbons, using a gamma-alumina-supported catalyst for comparison. These catalysts were used under pressure to conduct a distributive reaction and the desorbing behavior of CO or H/sub 2/ at elevated temperature was measured to examine the influence of the type of carrier or the method of preparation on the activity and the distribution of products formed. The WO/sub 3/-supported catalyst gave a carbon chain length distribution that did not comply with the rule of Schulz-Flory, giving a composition richer in the isomers. Carbon number distribution is affected by Ru-dispersion, and the selectivity of isomers depends on the acidity of the carrier. Formed products distribution of the WO/sub 3/-supported reaction is attributable to the secondary reaction, which relates to the acidic point of the carrier, of the primary product formed on the metal. (7 figs, 4 tabs, 18 refs)

Effects of Cu over Pd based catalysts supported on silica or niobia

Directory of Open Access Journals (Sweden)

Roma M.N.S.C.

2000-01-01

Full Text Available Palladium and palladium-copper catalysts supported on silica and niobia were characterized by H2 chemisorption and H2-O2 titration. Systems over silica were also analyzed by transmission electron microscopy and EXAFS. The metallic dispersion decreased from 20% to 7% when the content of Pd was increased from 0.5wt.-% to 3wt.-% in monometallic catalysts. The addition of 3 wt.-% Cu to obtain Pd-Cu catalysts caused a remarkable capacity loss of hydrogen chemisorption. TPR analysis suggested an interaction between the two metals and EXAFS characterization of the catalyst supported on silica confirmed the formation of Pd-Cu alloy. Pd/Nb2O5 catalysts showed turnover numbers higher than those obtained with the Pd/SiO2 systems in the cyclohexane dehydrogenation. However, the bimetallic catalysts showed very low turnover numbers.

Investigation of altenative carbon materials for fuel-cell catalyst support

DEFF Research Database (Denmark)

Larsen, Mikkel Juul

In order to ensure high utilization of the catalyst material in a polymer electrolyte membrane fuel cell (PEMFC) it is usually fixed in the form of nanoparticles on a supporting material. The catalyst is platinum or a platinum alloy, and the commonly used support is carbon black (CB). Although...... structured carbon forms such as graphitized CBs, carbon nanotubes (CNTs), and carbon nanofibres (CNFs). This thesis concerns the investigation of an array of different materials which may prospec-tively replace the conventional materials used in the catalyst. The study comprised 13 carbon samples which...... nanotubes (GMWCNTs), and graphitized carbon nanofibre (CNF), while the Pt/C samples were platinized samples of some of the CNTs and CNFs (Pt/FWCNT, Pt/GMWCNT, and Pt/CNF, respectively) as well as two commercial Pt/CB reference catalysts. Comparative analyses have been performed in order to be able to assess...

Selective hydrogenation of acetylene on SiO{sub 2} supported Ni-In bimetallic catalysts: Promotional effect of In

Energy Technology Data Exchange (ETDEWEB)

Chen, Yanjun; Chen, Jixiang, E-mail: jxchen@tju.edu.cn

2016-11-30

Graphical abstract: A suitable Ni/In ratio remarkably enhanced the acetylene conversion, the selectivity to ethylene and the catalyst stability. Display Omitted - Highlights: • There was a promotional effect of In on the performance of Ni/SiO{sub 2}. • A suitable Ni/In ratio was required for good performance of Ni{sub x}In/SiO{sub 2}. • Both geometrical and electronic effects of In contributed to good performance. • Ni/SiO{sub 2} deactivation is mainly owing to phase change from Ni to nickel carbide. • The carbonaceous deposit was the main reason for Ni{sub x}In/SiO{sub 2} deactivation. - Abstract: Ni/SiO{sub 2} and the bimetallic Ni{sub x}In/SiO{sub 2} catalysts with different Ni/In ratios were tested for the selective hydrogenation of acetylene, and their physicochemical properties before and after the reaction were characterized by means of N{sub 2}-sorption, H{sub 2}-TPR, XRD, TEM, XPS, H{sub 2} chemisorption, C{sub 2}H{sub 4}-TPD, NH{sub 3}-TPD, FT-IR of adsorbed pyridine, and TG/DTA and Raman. A promotional effect of In on the performance of Ni/SiO{sub 2} was found, and Ni{sub x}In/SiO{sub 2} with a suitable Ni/In ratio gave much higher acetylene conversion, ethylene selectivity and catalyst stability than Ni/SiO{sub 2}. This is ascribed to the geometrical isolation of the reactive Ni atoms with the inert In ones and the charge transfer from the In atoms to Ni ones, both of which are favorable for reducing the adsorption strength of ethylene and restraining the C−C hydrogenolysis and the polymerizations of acetylene and the intermediate compounds. On the whole, Ni{sub 6}In/SiO{sub 2} and Ni{sub 10}In/SiO{sub 2} had better performance. Nevertheless, with increasing the In content, the selectivity to the C4+ hydrocarbons tended to increase due to the enhanced catalyst acidity because of the charge transfer from the In atoms to Ni ones. As the Lewis acid ones, the In sites could promote the polymerization. The catalyst deactivation was also analyzed

EFFECT OF THE REDUCTION TEMPERATURE INTO CATALYTIC ACTIVITY OF Ni SUPPORTED BY TiO2, AL2O2 AND TiO2/AL2O3 FOR CONVERSION CO2 INTO METHANE

Directory of Open Access Journals (Sweden)

Hery Haerudin

2010-06-01

Full Text Available Nickel catalysts, containing 6% (w/w of nickel, have been prepared using TiO2, Al2O3 and mixture of TiO2-Al2O3 (1:9. The catalysts were used for CO2 conversion into methane. The characteristics of catalysts were studied by determination of its specific surface area, temperature programmed reaction technique and X-ray diffraction. The specific surface area were varied slightly by different temperature of reduction, namely after reduction at 300°C it was 39, 120 and 113 m2/g and after reduction at 400°C it was 42, 135  and 120 m2/g for 6% nickel catalysts supported on TiO2, Al2O3 and mixture of TiO2-Al2O3 (1:9 respectively. Temperature program reaction studies (TPO and TPR showed that NiTiOx species were possibly formed during the pretreatments which has shown by the shift of its peak to the lower temperature on Ni catalyst, that supported on mixture of TiO2-Al2O3 compared with catalysts supported on individual TiO2 or Al2O3. The nickel species on reduced Ni catalysts supported on TiO2 and on mixture of TiO2-Al2O3 could be detected by X-ray diffraction. The catalyst's activities toward CH4 formation were affected by the reduction temperature. Activity for CH4 formation was decreased in the following order: Ni/ TiO2 > Ni/ TiO2: Al2O3 > Ni/ Al2O3 and Ni/ TiO2: Al2O3 > Ni/ TiO2> Ni/ Al2O3, when catalysts were reduced at 300°C or 400°C respectively. The CO2 conversion was decreased in the following order: Ni/ Al2O3 > Ni/ TiO2: Al2O3 > Ni/ TiO2 when catalysts were reduced at 300°C or 400°C respectively.   Keywords: nickel catalyst, carbondioxide, methane

Continuous flow hydrogenation using polysilane-supported palladium/alumina hybrid catalysts

Directory of Open Access Journals (Sweden)

Shū Kobayashi

2011-05-01

Full Text Available Continuous flow systems for hydrogenation using polysilane-supported palladium/alumina (Pd/(PSi–Al2O3 hybrid catalysts were developed. Our original Pd/(PSi–Al2O3 catalysts were used successfully in these systems and the hydrogenation of unsaturated C–C bonds and a nitro group, deprotection of a carbobenzyloxy (Cbz group, and a dehalogenation reaction proceeded smoothly. The catalyst retained high activity for at least 8 h under neat conditions.

Graphitised Carbon Nanofibres as Catalyst Support for PEMFC

DEFF Research Database (Denmark)

Yli-Rantala, E.; Pasanen, A.; Kauranen, P.

2011-01-01

(PANI) precursor. The modified surfaces were studied by FTIR and XPS and the electrochemical characterization, including long-term Pt stability tests, was performed using a low-temperature PEMFC single cell. The performance and stability of the G-CNF supported catalysts were compared with a CB supported...

High hydrogen desorption properties of Mg-based nanocomposite at moderate temperatures: The effects of multiple catalysts in situ formed by adding nickel sulfides/graphene

Science.gov (United States)

Xie, Xiubo; Chen, Ming; Liu, Peng; Shang, Jiaxiang; Liu, Tong

2017-12-01

Nickel sulfides decorated reduced graphene oxide (rGO) has been produced by co-reducing Ni2+ and graphene oxide (GO), and is subsequently ball milled with Mg nanoparticles (NPs) produced by hydrogen plasma metal reaction (HPMR). The nickel sulfides of about 800 nm completely in situ change to MgS, Mg2Ni and Ni multiple catalysts after first hydrogenation/dehydrogenation process at 673 K. The Mg-5wt%NiS/rGO nanocomposite shows the highest hydrogen desorption kinetics and capacity properties, and the catalytic effect order of the additives is NiS/rGO, NiS and rGO. At 573 K, the Mg-NiS/rGO nanocomposite can quickly desorb 3.7 wt% H2 in 10 min and 4.5 wt% H2 in 60 min. The apparent hydrogen absorption and desorption activation energies of the Mg-5wt%NiS/rGO nanocomposite are decreased to 44.47 and 63.02 kJ mol-1, smaller than those of the Mg-5wt%rGO and Mg-5wt%NiS samples. The best hydrogen desorption properties of the Mg-5wt%NiS/rGO nanocomposite can be explained by the synergistic catalytic effects of the highly dispersed MgS, Mg2Ni and Ni catalysts on the rGO sheets, and the more nucleation sites between the catalysts, rGO sheets and Mg matrix.

Influence of ni addition to a low-loaded palladium catalyst on the selective hydrogenation of 1-heptyne

Directory of Open Access Journals (Sweden)

Cecilia R. Lederhos

2010-01-01

Full Text Available Semi-hydrogenation of alkynes has industrial and academic relevance on a large scale. To increase the activity, selectivity and lifetime of monometallic catalysts, the development of bimetallic catalysts has been investigated. 1-Heptyne hydrogenation over low-loaded Pd and Ni monometallic and PdNi bimetallic catalysts was studied in liquid phase at mild conditions. XPS results suggest that nickel addition to Pd modifies the electronic state of palladium as nickel loading is increased. Low-loaded Pd catalysts showed the highest selectivities (> 95%. The most active prepared catalyst, PdNi(1%, was more selective than the Lindlar catalyst.

Heterogeneous hydrogenation of unsaturated compounds with catalyst P-2-Ni with turnover numbers up to 90,000

Energy Technology Data Exchange (ETDEWEB)

Strohmeier, W; Pfoehler, M; Steigerwald, H [Wuerzburg Univ. (Germany, F.R.). Inst. fuer Physikalische Chemie

1977-12-01

Unsaturated compounds are very rapidly hydrogenated with nickel-boride catalyst P-2-Ni without solvent under mild conditions (70-85/sup 0/C and 10 bar). Turnover numbers UZ up to 90,000 and space-time-yields of 7.440 mmol product per l and 1 mgA Nickel in one hour with a mean catalyst activity a = 124 were observed. This hydrogenation catalyst has a power, which is in the same magnitude of very active noble metal catalysts.

Phosphorus poisoning of molybdenum sulfide hydrodesulfurization catalysts supported on carbon and alumina

NARCIS (Netherlands)

Bouwens, S.M.A.M.; Vissers, J.P.R.; Beer, de V.H.J.; Prins, R.

1988-01-01

Phosphorus-containing Mo sulfide catalysts supported on ¿-Al2O3 and activated carbon were evaluated for their thiophene HDS activities. Phosphorus was added as phosphoric acid to the carrier material prior to the molybdenum component. The thiophene HDS activity of the carbon-supported catalysts was

thesis of high-purity carbon nanotubes over alumina and silica supported bimetallic catalysts

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Sanja Ratković

2009-10-01

Full Text Available Carbon nanotubes (CNTs were synthesized by a catalytic chemical vapor deposition method (CCVD of ethylene over alumina and silica supported bimetallic catalysts based on Fe, Co and Ni. The catalysts were prepared by a precipitation method, calcined at 600 °C and in situ reduced in hydrogen flow at 700 °C. The CNTs growth was carried out by a flow the mixture of C2H4 and nitrogen over the catalyst powder in a horizontal oven. The structure and morphology of as-synthesized CNTs were characterized using SEM. The as-synthesized nanotubes were purified by acid and basic treatments in order to remove impurities such as amorphous carbon, graphite nanoparticles and metal catalysts. XRD and DTA/TG analyses showed that the amounts of by-products in the purified CNTs samples were reduced significantly. According to the observed results, ethylene is an active carbon source for growing high-density CNTs with high yield but more on alumina-supported catalysts than on their silica- supported counterparts. The last might be explained by SMSI formed in the case of alumina-supported catalysts, resulting in higher active phase dispersion.

Oligomerization of ethylene catalysed by nickel complexes associated with nitrogen ligands in ionic liquids; Oligomerisation de l'ethylene catalysee par des complexes du nickel associes a des ligands azotes dans les liquides ioniques

Energy Technology Data Exchange (ETDEWEB)

Lecocq, V.

2003-09-01

We report here the use of a new class of catalytic systems based on a nickel active center associated with nitrogen ligands, such as di-imines, or imino-pyridines, for the oligomerization of ethylene in a biphasic medium using ionic liquids as the catalyst solvent. The nickel catalyst is immobilized in the ionic liquid phase in which the olefinic reaction products are poorly miscible. This biphasic system makes possible an easy separation and recycle of the catalyst. Numerous di-imine and imino-pyridine ligands with different steric and electronic properties have been synthesized and their corresponding nickel complexes isolated and characterized. Different ionic liquids, based on chloro-aluminates or non-chloro-aluminates anions, have also been prepared and characterized. The effect of the nature of the ligand, the ionic liquid, the nickel precursor and its mode of activation have been studied and correlated with the selectivity and activity of the transformation of ethylene. (author)

A Study of Deactivating Carbon Species during Methanation on a Ni/Al₂O₃ Catalyst

DEFF Research Database (Denmark)

Olesen, Sine Ellemann

 natural gas and as the infrastructure is already in place for natural gas, it is an attractive alternative to depleting oil resources. Catalysts based on nickel are the most common choice within industry due to the relatively low price of nickel and its acceptable performance. However, nickel catalysts...

Recent Scientific Progress on Developing Supported Ni Catalysts for Dry (CO2 Reforming of Methane

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Hyun Ook Seo

2018-03-01

Full Text Available Two major green house gases (CO2 and CH4 can be converted into useful synthetic gas (H2 and CO during dry reforming of methane (DRM reaction, and a lot of scientific efforts has been made to develop efficient catalysts for dry reforming of methane (DRM. Noble metal-based catalysts can effectively assist DRM reaction, however they are not economically viable. Alternatively, non-noble based catalysts have been studied so far, and supported Ni catalysts have been considered as a promising candidate for DRM catalyst. Main drawback of Ni catalysts is its catalytic instability under operating conditions of DRM (>700 °C. Recently, it has been demonstrated that the appropriate choice of metal-oxide supports can address this issue since the chemical and physical of metal-oxide supports can prevent coke formation and stabilize the small Ni nanoparticles under harsh conditions of DRM operation. This mini-review covers the recent scientific findings on the development of supported Ni catalysts for DRM reaction, including the synthetic methods of supported Ni nanoparticles with high sintering resistance.

Selective hydrogenation of citral over supported Pt catalysts: insight into support effects

Energy Technology Data Exchange (ETDEWEB)

Wang, Xiaofeng [Missouri University of Science and Technology, Department of Chemical and Biochemical Engineering (United States); Hu, Weiming; Deng, Baolin [University of Missouri, Department of Civil and Environmental Engineering (United States); Liang, Xinhua, E-mail: liangxin@mst.edu [Missouri University of Science and Technology, Department of Chemical and Biochemical Engineering (United States)

2017-04-15

Highly dispersed platinum (Pt) nanoparticles (NPs) were deposited on various substrates by atomic layer deposition (ALD) in a fluidized bed reactor at 300 °C. The substrates included multi-walled carbon nanotubes (MWCNTs), silica gel (SiO{sub 2}), commercial γ-Al{sub 2}O{sub 3}, and ALD-prepared porous Al{sub 2}O{sub 3} particles (ALD-Al{sub 2}O{sub 3}). The results of TEM analysis showed that ~1.3 nm Pt NPs were highly dispersed on all different supports. All catalysts were used for the reaction of selective hydrogenation of citral to unsaturated alcohols (UA), geraniol, and nerol. Both the structure and acidity of supports affected the activity and selectivity of Pt catalysts. Pt/SiO{sub 2} showed the highest activity due to the strong acidity of SiO{sub 2} and the conversion of citral reached 82% after 12 h with a selectivity of 58% of UA. Pt/MWCNTs showed the highest selectivity of UA, which reached 65% with a conversion of 38% due to its unique structure and electronic effect. The cycling experiments indicated that Pt/MWCNTs and Pt/ALD-Al{sub 2}O{sub 3} catalysts were more stable than Pt/SiO{sub 2}, as a result of the different interactions between the Pt NPs and the supports.

Heterogeneous Pd catalysts supported on silica matrices

Czech Academy of Sciences Publication Activity Database

Opanasenko, Maksym; Štěpnička, P.; Čejka, Jiří

2014-01-01

Roč. 4, č. 110 (2014), s. 65137-65162 ISSN 2046-2069 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : catalysts * molecular sieves * palladium Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.840, year: 2014

Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

Energy Technology Data Exchange (ETDEWEB)

Mikolajczuk-Zychora, A., E-mail: amikolajczuk@ichf.edu.pl [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Borodzinski, A.; Kedzierzawski, P.; Mierzwa, B. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Mazurkiewicz-Pawlicka, M. [Faculty of Materials Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Faculty of Chemical and Process Engineering, Warsaw University of Technology, Warynskiego 1, Warsaw (Poland); Stobinski, L. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Faculty of Chemical and Process Engineering, Warsaw University of Technology, Warynskiego 1, Warsaw (Poland); Ciecierska, E. [Faculty of Materials Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Zimoch, A.; Opałło, M. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland)

2016-12-01

Highlights: • Palladium catalyst used on the cathode DFAFC is comparable to commercial platinum catalyst. • The treatment of carbon supports in nitric acid(V) increases the electrochemically available metal surface area and the catalytic activity in oxygen reduction reaction of catalysts. - Abstract: One of the drawbacks of low-temperature fuel cells is high price of platinum-based catalysts used for the electroreduction of oxygen at the cathode of the fuel cell. The aim of this work is to develop the palladium catalyst that will replace commonly used platinum cathode catalysts. A series of palladium catalysts for oxygen reduction reaction (ORR) were prepared and tested on the cathode of Direct Formic Acid Fuel Cell (DFAFC). Palladium nanoparticles were deposited on the carbon black (Vulcan) and on multiwall carbon nanotubes (MWCNTs) surface by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as a reducing agent. The effect of functionalization of the carbon supports on the catalysts physicochemical properties and the ORR catalytic activity on the cathode of DFAFC was studied. The supports were functionalized by treatment in nitric acid for 4 h at 80 °C. The structure of the prepared catalysts has been characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV). Hydrophilicity of the catalytic layers was determined by measuring contact angles of water droplets. The performance of the prepared catalysts has been compared with that of the commercial 20 wt.% Pt/C (Premetek) catalyst. The maximum power density obtained for the best palladium catalyst, deposited on the surface of functionalized carbon black, is the same as that for the commercial Pt/C (Premetek). Palladium is cheaper than platinum, therefore the developed cathode catalyst is promising for future applications.

A phenyl-sulfonic acid anchored carbon-supported platinum catalyst for polymer electrolyte fuel cell electrodes

International Nuclear Information System (INIS)

Selvarani, G.; Sahu, A.K.; Choudhury, N.A.; Sridhar, P.; Pitchumani, S.; Shukla, A.K.

2007-01-01

A method, to anchor phenyl-sulfonic acid functional groups with the platinum catalyst supported onto a high surface-area carbon substrate, is reported. The use of the catalyst in the electrodes of a polymer electrolyte fuel cell (PEFC) helps enhancing its performance. Characterization of the catalyst by Fourier transform infra red (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and point-of-zero-charge (PZC) studies suggests that the improvement in performance of the PEFC is facilitated not only by enlarging the three-phase boundary in the catalyst layer but also by providing ionic-conduction paths as well as by imparting negative charge to platinum sites with concomitant oxidation of sulfur present in the carbon support. It is argued that the negatively charged platinum sites help repel water facilitating oxygen to access the catalyst sites. The PEFC with modified carbon-supported platinum catalyst electrodes exhibits 40% enhancement in its power density as compared to the one with unmodified carbon-supported platinum catalyst electrodes

Evaluation of alumina-aluminium phosphate catalyst supports for hydrodenitrogenation of pyridine and coal-derived liquids

Energy Technology Data Exchange (ETDEWEB)

Menon, R.; Joo, H.S.; Guin, J.A.; Reucroft, P.J.; Kim, J.Y. [Auburn University, Auburn, AL (United States). Dept. of Chemical Engineering

1996-05-01

Several alumina-aluminum phosphate (AAP) catalyst supports were prepared by a coprecipitation method. Effect of variations in Al/P atomic ratios on support textural properties were examined. Finished NiMo/AAP catalysts containing nominally 3 wt% Ni and 13 wt% Mo were prepared by incipient wetness and characterized by several methods including elemental, BET, and XPS surface analysis. Initial hydrodenitrogenation (HDN) activities of the catalysts were examined in both pyridine model compound and coal liquid reactions. The AAP supports showed the opportunity to tailor the catalyst pore size by variation of the Al/P ratio. On a per unit surface areas basis, the AAP-supported catalysts had initial HDN activities comparable to those of a commercial P-promoted NiMo/Al{sub 2}O{sub 3} catalyst. Because of their unique textural properties, i.e. variable pore sizes, the AAP catalysts may offer advantages when dealing with macromolecular feedstocks where hindered diffusion may slow reaction rates. 37 refs., 8 figs., 6 tabs.

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

DEFF Research Database (Denmark)

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

2011-01-01

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

The generation of efficient supported (Heterogeneous) olefin metathesis catalysts

Energy Technology Data Exchange (ETDEWEB)

Grubbs, Robert H

2013-04-05

Over the past decade, a new family of homogeneous metathesis catalysts has been developed that will tolerate most organic functionalities as well as water and air. These homogeneous catalysts are finding numerous applications in the pharmaceutical industry as well as in the production of functional polymers. In addition the catalysts are being used to convert seed oils into products that can substitute for those that are now made from petroleum products. Seed oils are unsaturated, contain double bonds, and are a ready source of linear hydrocarbon fragments that are specifically functionalized. To increase the number of applications in the area of biomaterial conversion to petrol chemicals, the activity and efficiency of the catalysts need to be as high as possible. The higher the efficiency of the catalysts, the lower the cost of the conversion and a larger number of practical applications become available. Active supported catalysts were prepared and tested in the conversion of seed oils and other important starting materials. The outcome of the work was successful and the technology has been transferred to a commercial operation to develop viable applications of the discovered systems. A biorefinery that converts seed oils is under construction in Indonesia. The catalysts developed in this study will be considered for the next generation of operations.

Allotropic Carbon Nanoforms as Advanced Metal-Free Catalysts or as Supports

Directory of Open Access Journals (Sweden)

Hermenegildo Garcia

2014-01-01

Full Text Available This perspective paper summarizes the use of three nanostructured carbon allotropes as metal-free catalysts (“carbocatalysts” or as supports of metal nanoparticles. After an introductory section commenting the interest of developing metal-free catalysts and main features of carbon nanoforms, the main body of this paper is focused on exemplifying the opportunities that carbon nanotubes, graphene, and diamond nanoparticles offer to develop advanced catalysts having active sites based on carbon in the absence of transition metals or as large area supports with special morphology and unique properties. The final section provides my personal view on future developments in this field.

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

International Nuclear Information System (INIS)

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

2016-01-01

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

Highly selective oxidative dehydrogenation of ethane with supported molten chloride catalysts

Energy Technology Data Exchange (ETDEWEB)

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

2011-07-01

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

Influence of silica-alumina support ratio on H2 production and catalyst carbon deposition from the Ni-catalytic pyrolysis/reforming of waste tyres.

Science.gov (United States)

Zhang, Yeshui; Tao, Yongwen; Huang, Jun; Williams, Paul

2017-10-01

The influence of catalyst support alumina-silica in terms of different Al 2 O 3 to SiO 2 mole ratios containing 20 wt.% Ni on the production of hydrogen and catalyst coke formation from the pyrolysis-catalysis of waste tyres is reported. A two-stage reactor system was used with pyrolysis of the tyres followed by catalytic reaction. There was only a small difference in the total gas yield and hydrogen yield by changing the Al 2 O 3 to SiO 2 mole ratios in the Ni-Al 2 O 3 /SiO 2 catalyst. The 1:1 ratio of Al 2 O 3 :SiO 2 ratio produced the highest gas yield of 27.3 wt.% and a hydrogen production of 14.0 mmol g -1 tyre . Catalyst coke formation decreased from 19.0 to 13.0 wt.% as the Al 2 O 3 :SiO 2 ratio was changed from 1:1 to 2:1, with more than 95% of the coke being filamentous-type carbon, a large proportion of which was multi-walled carbon nanotubes. Further experiments introduced steam to the second-stage reactor to investigate hydrogen production for the pyrolysis-catalytic steam reforming of the waste tyres using the 1:1 Al 2 O 3 /SiO 2 nickel catalyst. The introduction of steam produced a marked increase in total gas yield from ~27 wt. % to ~58 wt.%; in addition, hydrogen production was increased to 34.5 mmol g -1 and there was a reduction in catalyst coke formation to 4.6 wt.%.

Influence of silica–alumina support ratio on H2 production and catalyst carbon deposition from the Ni-catalytic pyrolysis/reforming of waste tyres

Science.gov (United States)

Zhang, Yeshui; Tao, Yongwen; Huang, Jun; Williams, Paul

2017-01-01

The influence of catalyst support alumina–silica in terms of different Al2O3 to SiO2 mole ratios containing 20 wt.% Ni on the production of hydrogen and catalyst coke formation from the pyrolysis-catalysis of waste tyres is reported. A two-stage reactor system was used with pyrolysis of the tyres followed by catalytic reaction. There was only a small difference in the total gas yield and hydrogen yield by changing the Al2O3 to SiO2 mole ratios in the Ni-Al2O3/SiO2 catalyst. The 1:1 ratio of Al2O3:SiO2 ratio produced the highest gas yield of 27.3 wt.% and a hydrogen production of 14.0 mmol g-1tyre. Catalyst coke formation decreased from 19.0 to 13.0 wt.% as the Al2O3:SiO2 ratio was changed from 1:1 to 2:1, with more than 95% of the coke being filamentous-type carbon, a large proportion of which was multi-walled carbon nanotubes. Further experiments introduced steam to the second-stage reactor to investigate hydrogen production for the pyrolysis-catalytic steam reforming of the waste tyres using the 1:1 Al2O3/SiO2 nickel catalyst. The introduction of steam produced a marked increase in total gas yield from ~27 wt. % to ~58 wt.%; in addition, hydrogen production was increased to 34.5 mmol g-1 and there was a reduction in catalyst coke formation to 4.6 wt.%. PMID:28789599

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

Dehydrogenation of Isobutane with Carbon Dioxide over SBA-15-Supported Vanadium Oxide Catalysts

Directory of Open Access Journals (Sweden)

Chunling Wei

2016-10-01

Full Text Available A series of vanadia catalysts supported on SBA-15 (V/SBA with a vanadia (V content ranging from 1% to 11% were prepared by an incipient wetness method. Their catalytic behavior in the dehydrogenation of isobutane to isobutene with CO2 was examined. The catalysts were characterized by N2 adsorption, X-ray diffraction (XRD, scanning electron microscopy (SEM, Raman spectroscopy, and temperature-programmed reduction (TPR. It was found that these catalysts were effective for the dehydrogenation reaction, and the catalytic activity is correlated with the amount of dispersed vanadium species on the SBA-15 support. The 7% V/SBA catalyst shows the highest activity, which gives 40.8% isobutane conversion and 84.8% isobutene selectivity. The SBA-15-supported vanadia exhibits higher isobutane conversion and isobutene selectivity than the MCM-41-supported one.

Modification by SiO2 of Alumina Support for Light Alkane Dehydrogenation Catalysts

Directory of Open Access Journals (Sweden)

Giyjaz E. Bekmukhamedov

2016-10-01

Full Text Available Due to the continuously rising demand for C3–C5 olefins it is important to improve the performance of catalysts for dehydrogenation of light alkanes. In this work the effect of modification by SiO2 on the properties of the alumina support and the chromia-alumina catalyst was studied. SiO2 was introduced by impregnation of the support with a silica sol. To characterize the supports and the catalysts the following techniques were used: low-temperature nitrogen adsorption; IR-spectroscopy; magic angle spinning 29Si nuclear magnetic resonance; temperature programmed desorption and reduction; UV-Vis-, Raman- and electron paramagnetic resonance (EPR-spectroscopy. It was shown that the modifier in amounts of 2.5–7.5 wt % distributed on the support surface in the form of SiOx-islands diminishes the interaction between the alumina support and the chromate ions (precursor of the active component. As a result, polychromates are the compounds predominantly stabilized on the surface of the modified support; under thermal activation of the catalyst and are reduced to the amorphous Cr2O3. This in turn leads to an increase in the activity of the catalyst in the dehydrogenation of isobutane.

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

Hydrodechlorination of Tetrachloromethane over Palladium Catalysts Supported on Mixed MgF2-MgO Carriers

Directory of Open Access Journals (Sweden)

Magdalena Bonarowska

2016-11-01

Full Text Available Pd/MgO, Pd/MgF2 and Pd/MgO-MgF2 catalysts were investigated in the reaction of CCl4 hydrodechlorination. All the catalysts deactivated in time on stream, but the degree of deactivation varied from catalyst to catalyst. The MgF2-supported palladium with relatively large metal particles appeared the best catalyst, characterized by good activity and selectivity to C2-C5 hydrocarbons. Investigation of post-reaction catalyst samples allowed to find several details associated with the working state of hydrodechlorination catalysts. The role of support acidity was quite complex. On the one hand, a definite, although not very high Lewis acidity of MgF2 is beneficial for shaping high activity of palladium catalysts. The MgO-MgF2 support characterized by stronger Lewis acidity than MgF2 contributes to very good catalytic activity for a relatively long reaction period (~5 h but subsequent neutralization of stronger acid centers (by coking eliminates them from the catalyst. On the other hand, the role of acidity evolution, which takes place when basic supports (like MgO are chlorided during HdCl reactions, is difficult to assess because different events associated with distribution of chlorided support species, leading to partial or even full blocking of the surface of palladium, which plays the role of active component in HdCl reactions.

Polyvinylpolypyrrolidone Supported Brønsted Acidic Catalyst for Esterification

Directory of Open Access Journals (Sweden)

Song Wang

2016-01-01

Full Text Available A polyvinylpolypyrrolidone (PVPP supported Brønsted acidic catalyst ([PVPP-BS]HSO4 was prepared by coupling SO3H-functionalized polyvinylpolypyrrolidone with H2SO4 in this work. After the characterization through FT-IR, FESEM, TG, BET, and elemental analysis, it was found that 1,4-butane sultone (BS and sulfuric acid reacted with PVPP and were immobilized on PVPP surface. The prepared [PVPP-BS]HSO4 catalyst shows high catalytic activity for a series of esterification reactions and could be separated from the reacted mixture easily. Moreover, this catalyst could be recycled and reused for six times without significant loss of catalytic performance.

Hydrogenation of naphthalene on NiMo- Ni- and Ru/Al{sub 2}O{sub 3} catalysts. Langmuir-Hinshelwood kinetic modelling

Energy Technology Data Exchange (ETDEWEB)

Monteiro-Gezork, Ana Cristina Alves; Winterbottom, John Mike [Department of Chemical Engineering, School of Engineering, The University of Birmingham, Birmingham B15 2TT (United Kingdom); Natividad, Reyna [Department of Chemical Engineering, Faculty of Chemistry, Universidad Autonoma del Estado de Mexico, Paseo Colon Esq. Tollocan, Toluca, Edo. de Mexico, Mexico CP 50120 (Mexico)

2008-01-30

The importance of the hydrodearomatisation (HDA) is increasing together with tightening legislation of fuel quality and exhaust emissions. The present study focuses on hydrogenation (HYD) kinetics of the model aromatic compound naphthalene, found in typical diesel fraction, in n-hexadecane over a NiMo (nickel molybdenum), Ni (nickel) and Ru (ruthenium) supported on trilobe alumina (Al{sub 2}O{sub 3}) catalysts. Kinetic reaction expressions based on the mechanistic Langmuir-Hinshelwood (L-H) model were derived and tested by regressing the experimental data that translated the effect of both naphthalene and hydrogen concentration at a constant temperature (523.15 and 573.15 K over the NiMo catalyst and at 373.15 K over the Ni and Ru/Al{sub 2}O{sub 3} catalysts) on the initial reaction rate. The L-H equation, giving an adequate fit to the experimental data with physically meaningful parameters, suggested a competitive adsorption between hydrogen and naphthalene over the presulphided NiMo catalyst and a non-competitive adsorption between these two reactants over the prereduced Ni and Ru/Al{sub 2}O{sub 3} catalysts. In addition, the adsorption constant values indicated that the prereduced Ru catalyst was a much more active catalyst towards naphthalene HYD than the prereduced Ni/Al{sub 2}O{sub 3} or the presulphided NiMo/Al{sub 2}O{sub 3} catalyst. (author)

SELECTIVE HYDROGENATION OF CINNAMALDEHYDE WITH Pt AND Pt-Fe CATALYSTS: EFFECTS OF THE SUPPORT

Directory of Open Access Journals (Sweden)

A.B. da Silva

1998-06-01

Full Text Available Low-temperature reduced TiO2-supported Pt and Pt-Fe catalysts are much more active and selective for the liquid–phase hydrogenation of cinnamaldehyde to unsaturated cinnamyl alcohol than the corresponding carbon-supported catalysts. High-temperature reduced catalysts, where the SMSI effect should be present, are almost inactive for this reaction. There is at present no definitive explanation for this effect but an electronic metal-support interaction is most probably involved.

CO2 methanation on the catalyst of Ni/MCM-41 promoted with CeO2.

Science.gov (United States)

Wang, Xiaoliu; Zhu, Lingjun; Liu, Yincong; Wang, Shurong

2018-06-01

CO 2 as a raw feed combined with renewable hydrogen for the production of useful chemicals and alternative energy products is one of the solutions to environmental and energy problems. In this study, a series of Ni-xCeO 2 /MCM-41 catalysts with a nickel content of 20wt% were prepared through deposition precipitation method for CO 2 methanation. Different characterization methods, including BET, XRD, TEM, SEM, H 2 -TPR and H 2 -TPD were applied to help explore the influence mechanism of CeO 2 on Ni/MCM-41 in CO 2 methanation. It was found that all CeO 2 -promoted catalysts exhibited enhanced catalytic activity when compared to Ni/MCM-41. The catalyst modified with 20wt% CeO 2 showed the best catalytic performance, with CO 2 conversion and CH 4 selectivity of 85.6% and 99.8%, respectively, at the temperature of 380°C under atmospheric pressure. The synergetic effects among Ni 0 active sites, the promoter and the support, including nickel dispersion improvement and increased CO 2 adsorption sites due to the addition of CeO 2 , were considered as important factors for high reactivity of the promoted catalysts. The stability test showed that the promoted catalyst maintained its high reactivity after 30h. Copyright © 2017 Elsevier B.V. All rights reserved.

Nickel foam-supported polyaniline cathode prepared with electrophoresis for improvement of rechargeable Zn battery performance

Science.gov (United States)

Xia, Yang; Zhu, Derong; Si, Shihui; Li, Degeng; Wu, Sen

2015-06-01

Porous nickel foam is used as a substrate for the development of rechargeable zinc//polyaniline battery, and the cathode electrophoresis of PANI microparticles in non-aqueous solution is applied to the fabrication of Ni foam supported PANI electrode, in which the corrosion of the nickel foam substrate is prohibited. The Ni foam supported PANI cathode with high loading is prepared by PANI electrophoretic deposition, and followed by PANI slurry casting under vacuum filtration. The electrochemical charge storage performance for PANI material is significantly improved by using nickel foam substrate via the electrophoretic interlayer. The specific capacity of the nickel foam-PANI electrode with the electrophoretic layer is higher than the composite electrode without the electrophoretic layer, and the specific capacity of PANI supported by Ni foam reaches up to 183.28 mAh g-1 at the working current of 2.5 mA cm-2. The present electrophoresis deposition method plays the facile procedure for the immobilization of PANI microparticles onto the surface of non-platinum metals, and it becomes feasible to the use of the Ni foam supported PANI composite cathode for the Zn/PANI battery in weak acidic electrolyte.

Preparation by thermal evaporation under vacuum of thin nickel films without support

International Nuclear Information System (INIS)

Prugne, P.; Garin, P.; Lechauguette, G.

1959-01-01

This note deals with the preparation of nickel films without support by means of the technique described but using a new evaporation apparatus. In effect it was necessary, in order to obtain these nickel films, to modify the thermal evaporation conditions. An attempt to obtain a film without support after evaporation in a conventional apparatus led almost invariably to defeat. This appeared to be due to the high concentration of oxygen and of various vapors (diffusion pumps, degassing, etc.) present in the residual atmosphere of the conventional evaporation system. Reprint of a paper published in 'Le Vide, N. 74, March-April 1958, p. 82-83

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.

Support acidity influence in NiMoS (Nickel and Molybdenum) catalyst for Marlim diesel; Influencia da acidez do suport de catalisadores NiMoS (Niquel e Molibidenio) no hidrotratamento de diesel Marlim

Energy Technology Data Exchange (ETDEWEB)

Ferraz, Sheila Guimaraes de Almeida; Zotin, Jose Luiz; Jesus, Anderson Gomes de; Santos, Bruno Martins; Medeiros, Marcus Vinicius Costa [PETROBRAS S.A., Rio de Janeiro, RJ (Brazil). Centro de Pesquisas (CENPES)

2008-07-01

The specification of diesel points to the reduction of the sulfur content, of the final boiling point, of the density range and increase of the cetane number. These two last properties are directly related with the ability of the hydrotreating catalytic system in promoting the hydrogenation of aromatic structures and ring opening of the naphthenic compounds, which are both associated to low cetane number. In such way, more acidic catalysts, able to promote the cracking of naphthenic structures, should be evaluated for the diesel HDT. Three bifunctional NiMo catalysts with the same metal content, different acidity and similar active phase dispersion were prepared using alumina, silica-alumina and alumina-Y zeolite as supports. These catalysts were evaluated in a micro-reactor unit for diesel HDT aiming to correlate their activity with the support acidity. The alumina and alumina-zeolite supported catalysts presented better performance than the one supported on silica-alumina. NiMo/alumina-zeolite showed higher cetane and density improvement, associated with a slight decrease in the initial boiling point. (author)

Does airborne nickel exposure induce nickel sensitization?

Science.gov (United States)

Mann, Eugen; Ranft, Ulrich; Eberwein, Georg; Gladtke, Dieter; Sugiri, Dorothee; Behrendt, Heidrun; Ring, Johannes; Schäfer, Torsten; Begerow, Jutta; Wittsiepe, Jürgen; Krämer, Ursula; Wilhelm, Michael

2010-06-01

Nickel is one of the most prevalent causes of contact allergy in the general population. This study focuses on human exposure to airborne nickel and its potential to induce allergic sensitization. The study group consisted of 309 children at school-starter age living in the West of Germany in the vicinity of two industrial sources and in a rural town without nearby point sources of nickel. An exposure assessment of nickel in ambient air was available for children in the Ruhr district using routinely monitored ambient air quality data and dispersion modelling. Internal nickel exposure was assessed by nickel concentrations in morning urine samples of the children. The observed nickel sensitization prevalence rates varied between 12.6% and 30.7%. Statistically significant associations were showed between exposure to nickel in ambient air and urinary nickel concentration as well as between urinary nickel concentration and nickel sensitization. Furthermore, an elevated prevalence of nickel sensitization was associated with exposure to increased nickel concentrations in ambient air. The observed associations support the assumption that inhaled nickel in ambient air might be a risk factor for nickel sensitization; further studies in larger collectives are necessary.

Supported Catalysts Useful in Ring-Closing Metathesis, Cross Metathesis, and Ring-Opening Metathesis Polymerization

Directory of Open Access Journals (Sweden)

Jakkrit Suriboot

2016-04-01

Full Text Available Ruthenium and molybdenum catalysts are widely used in synthesis of both small molecules and macromolecules. While major developments have led to new increasingly active catalysts that have high functional group compatibility and stereoselectivity, catalyst/product separation, catalyst recycling, and/or catalyst residue/product separation remain an issue in some applications of these catalysts. This review highlights some of the history of efforts to address these problems, first discussing the problem in the context of reactions like ring-closing metathesis and cross metathesis catalysis used in the synthesis of low molecular weight compounds. It then discusses in more detail progress in dealing with these issues in ring opening metathesis polymerization chemistry. Such approaches depend on a biphasic solid/liquid or liquid separation and can use either always biphasic or sometimes biphasic systems and approaches to this problem using insoluble inorganic supports, insoluble crosslinked polymeric organic supports, soluble polymeric supports, ionic liquids and fluorous phases are discussed.

Support effects on hydrotreating activity of NiMo catalysts

International Nuclear Information System (INIS)

Dominguez-Crespo, M.A.; Arce-Estrada, E.M.; Torres-Huerta, A.M.; Diaz-Garcia, L.; Cortez de la Paz, M.T.

2007-01-01

The effect of the gamma alumina particle size on the catalytic activity of NiMoS x catalysts prepared by precipitation method of aluminum acetate at pH = 10 was studied. The structural characterization of the supports was measured by using XRD, pyridine FTIR-TPD and nitrogen physisorption. NiMo catalysts were characterized during the preparation steps (annealing and sulfidation) using transmission electron microscopy (TEM). Hydrogen TPR studies of the NiMo catalysts were also carried out in order to correlate their hydrogenating properties and their catalytic functionality. Catalytic tests were carried out in a pilot plant at 613, 633 and 653 K temperatures. The results showed that the rate constants of hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatizing (HDA) at 613-653 K decreased in the following order: A > B > C corresponding to the increase of NiMoS particle size associated to these catalysts

Evidence for H2/D2 isotope effects on Fischer-Tropsch synthesis over supported ruthenium catalysts

International Nuclear Information System (INIS)

Kellner, C.S.; Bell, A.T.

1981-01-01

The effects of using D 2 rather than H 2 during Fischer-Tropsch synthesis were investigated using alumina- and silica-supported Ru catalysts. For the alumina-supported catalysts, the rate of CD 4 formation was 1.4 to 1.6 times faster than the formation of CH 4 . A noticeable isotope effect was also observed for higher molecular weight products. The magnitude of the isotope effects observed using the silica-supported catalyst was much smaller than that found using the alumina-supported catalysts. The formation of olefins relative to paraffins was found to be higher when H 2 rather than D 2 was used, independent of the catalyst support. The observed isotope effects are explained in terms of a mechanism for CO hydrogenation and are shown to arise from a complex combination of the kinetic and equilibrium isotope effects associated with elementary processes occurring on the catalyst surface

Catalyst study for the plasma exhaust purification process

International Nuclear Information System (INIS)

Chabot, J.; Sannier, J.

1990-01-01

Several catalysts available from commercial sources have been screened to find out specific catalysts which allow complete methane oxidation and ammonia decomposition at temperature as low as possible in order to minimize tritium loss by permeation through processing equipment walls. Afterwards, an extended kinetic investigation has been performed on the best catalysts to achieve the data necessary to unit calculations. For methane oxidation, a palladium on alumina catalyst shows a very satisfactory low-temperature efficiency while a non-precious metal catalyst made of nickel oxide and alumina was found to be the more efficient for ammonia decomposition

XRD (X-Ray Diffraction) and nitrogen adsorption characterization of Ni-Pt/mordenite catalysts; Caracterizacao por EDX (Espectrometria de Raios-X), DRX (Difracao de Raios-X) e adsorcao de nitrogenio de catalisadores Ni/Pt/mordenita visando sua aplicacao na isomerizacao de n-hexano

Energy Technology Data Exchange (ETDEWEB)

Martins, Geovana do Socorro V.; Sousa, Bianca V.; Rodrigues, Meiry Glaucia F. [Universidade Federal de Campina Grande (UFCG), PB (Brazil)

2008-07-01

The search for molecules of high octane arose great interest in the isomerization processes. Catalysts to the zeolite base have been wide developed for the n-paraffins isomerization. In this work, bimetallic bifunctional catalysts supported on Mordenite zeolite were prepared samples containing 60Pt40Ni (wt.%) metal (Pt). The catalysts were obtained by competitive ion exchange using aqueous solutions of [Pt(NH{sub 3}){sub 4}]Cl{sub 2} and Ni(NH{sub 3}){sub 6}]Cl{sub 2} complexes. The EDS characterization analyses showed incorporation of the nickel and platinum mordenite zeolite. The diffractograms showed competitive ion exchange and calcination processes did not provoke appreciable changes in the zeolitic support framework. The peaks attributed to nickel and platinum oxides was possible to observe in the bimetallic catalysts 60Ni40Pt/MOR. The results of the N{sub 2} physical adsorption of the 60Ni40Pt/MOR showed that it did not have modification in the superficial area of the catalysts. (author)

Carbon nanostructures as catalyst support for polymer electrolyte membrane fuel cells

Energy Technology Data Exchange (ETDEWEB)

Natarajan, S.K.; Hamelin, J. [Quebec Univ., Trois Rivieres, PQ (Canada). Inst. de recherche sur l' hydrogene

2008-07-01

This paper reported on a study that investigated potential alternatives to Vulcan XC-72 as a catalyst supports for polymer electrolyte membrane fuel cells (PEMFCs). These included carbon nanostructures (CNS) prepared by high energy ball milling of graphite and transition metal catalysts, followed by heat treatment. Among the key factors discussed were the graphitic content, high surface area, microporous structure, good electrical conductivity and the ability of the material to attach functional groups. Some graphic results supporting the usage of CNS as catalyst support for PEMFCs were presented. Upon chemical oxidation, surface functional groups such as carbonyl, carboxyl, and hydroxyl were populated on the surface of CNS. Nanosized platinum particles with particle size distribution between 3 nm and 5 nm were reduced on the functionalized sites of CNS in a colloidal medium. The paper also presented cyclic voltammograms, XPS, HRTEM and PSD results. 3 refs.

Steam Reforming of Acetic Acid over Co-Supported Catalysts: Coupling Ketonization for Greater Stability

Energy Technology Data Exchange (ETDEWEB)

Davidson, Stephen D. [Energy and Environmental; Spies, Kurt A. [Energy and Environmental; Mei, Donghai [Energy and Environmental; Kovarik, Libor [Energy and Environmental; Kutnyakov, Igor [Energy and Environmental; Li, Xiaohong S. [Energy and Environmental; Lebarbier Dagle, Vanessa [Energy and Environmental; Albrecht, Karl O. [Energy and Environmental; Dagle, Robert A. [Energy and Environmental

2017-09-11

We report on the markedly improved stability of a novel 2-bed catalytic system, as compared to a conventional 1-bed steam reforming catalyst, for the production of H2 from acetic acid. The 2-bed catalytic system comprises of i) a basic oxide ketonization catalyst for the conversion of acetic acid to acetone, and a ii) Co-based steam reforming catalyst, both catalytic beds placed in sequence within the same unit operation. Steam reforming catalysts are particularly prone to catalytic deactivation when steam reforming acetic acid, used here as a model compound for the aqueous fraction of bio-oil. Catalysts comprising MgAl2O4, ZnO, CeO2, and activated carbon (AC) both with and without Co-addition were evaluated for conversion of acetic acid and acetone, its ketonization product, in the presence of steam. It was found that over the bare oxide support only ketonization activity was observed and coke deposition was minimal. With addition of Co to the oxide support steam reforming activity was facilitated and coke deposition was significantly increased. Acetone steam reforming over the same Co-supported catalysts demonstrated more stable performance and with less coke deposition than with acetic acid feedstock. DFT analysis suggests that over Co surface CHxCOO species are more favorably formed from acetic acid versus acetone. These CHxCOO species are strongly bound to the Co catalyst surface and could explain the higher propensity for coke formation from acetic acid. Based on these findings, in order to enhance stability of the steam reforming catalyst a dual-bed (2-bed) catalyst system was implemented. Comparing the 2-bed and 1-bed (Co-supported catalyst only) systems under otherwise identical reaction conditions the 2-bed demonstrated significantly improved stability and coke deposition was decreased by a factor of 4.

Dimethyl carbonate synthesis via transesterification of propylene carbonate with methanol by ceria-zinc catalysts: Role of catalyst support and reaction parameters

Energy Technology Data Exchange (ETDEWEB)

Kumar, Praveen; Srivastava, Vimal Chandra; Mishra, Indra Mani [Indian Institute of Technology Roorkee, Roorkee 247667, Uttarakhand (India)

2015-09-15

Ceria and zinc oxide catalyst were impregnated onto various oxide supports, namely Al{sub 2}O{sub 3}, TiO{sub 2} and SiO{sub 2}, individually by deposition-coprecipitation method. The synthesized catalysts (CZA, CZS and CZT having supports Al{sub 2}O{sub 3}, TiO{sub 2} and SiO{sub 2}, respectively) were characterized by X-ray diffraction (XRD), NH{sub 3}- and CO{sub 2}-temperature programmed desorption (TPD) and N2 adsorption. These catalysts were used for synthesis of dimethyl carbonate (DMC) from methanol and propylene carbonate in a batch reactor. CZS was found to have larger average grain size as compared to CZA and CZT. Composite oxides (catalysts) were found to contain individual phases of ZnO, CeO{sub 2} and some spinel forms of Zn, Ce along with their supports. CZS having highest basicity and surface area showed better catalytic activity as compared to CZA and CZT. Effect of reaction temperature and methanol/PC molar ratio on DMC yield was studied and a reaction mechanism has been discussed. Maximum DMC yield of 77% was observed with CZS catalyst at 170 .deg. C with methanol/PC molar ratio of 10.

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

Science.gov (United States)

Cavendish, Rio

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

New insides in the characterization of HDS industrial catalysts by HAADF-STEM

Science.gov (United States)

Del Angel, Paz; Ponce, Arturo; Arellano, Josefina; Yacaman, Miguel J.; Hernandez-Pichardo, Martha; Montoya, J. Ascencion; Escobar, Jose

2015-03-01

Hydrodesulfurization (HDS) catalysts are of great importance in the petroleum industry. Transition metal sulphides catalysts of Ni(Co)Mo(W)/Al2O3 are widely used for hydrotreating reactions, like hydrodenitrogenation and HDS. One of the main issue in these catalysts is to understand the mechanism of the reaction, where MoS2 plays the most important role in the catalytic activity. We studied an industrial NiMo/Alumina sulfide catalyst highly active by using aberration-corrected HAADF-STEM techniques. The used catalysts was a state-of- the art commercial nickel-molybdenum alumina-supported formulation, including organic agent modifier. This type of material belongs to a novel family of catalysts specially designed for ultra-low sulfur production from straight-run gas oil (SRGO), cycle oil, coker gas oil, or their combinations at operating conditions of commercial interest in hydrotreating units at industrial scale. Aberration corrected HAADF-STEM allowed to observe the nanostructure and location of MoS2 and his interaction with the alumina. The results indicate that the MoS2 is highly dispersed on the alumina, however the location of Ni is one of the task of this kind of catalyst.

Hydroprocessing using regenerated spent heavy hydrocarbon catalyst

International Nuclear Information System (INIS)

Clark, F.T.; Hensley, A.L. Jr.

1992-01-01

This patent describes a process for hydroprocessing a hydrocarbon feedstock. It comprises: contacting the feedstock with hydrogen under hydroprocessing conditions with a hydroprocessing catalyst wherein the hydroprocessing catalyst contains a total contaminant metals build-up of greater than about 4 wt. % nickel plus vanadium, a hydrogenation component selected from the group consisting of Group VIB metals and Group VIII metals and is regenerated spent hydroprocessing catalyst regenerated by a process comprising the steps: partially decoking the spent catalyst in an initial coke-burning step; impregnating the partially decoked catalyst with a Group IIA metal-containing impregnation solution; and decoking the impregnated catalyst in a final coke-burning step wherein the impregnated catalyst is contacted with an oxygen-containing gas at a temperature of about 600 degrees F to about 1400 degrees F

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.

Physicochemical investigations of carbon nanofiber supported Cu/ZrO2 catalyst

International Nuclear Information System (INIS)

Din, Israf Ud; Shaharun, Maizatul S.; Subbarao, Duvvuri; Naeem, A.

2014-01-01

Zirconia-promoted copper/carbon nanofiber catalysts (Cu‐ZrO 2 /CNF) were prepared by the sequential deposition precipitation method. The Herringbone type of carbon nanofiber GNF-100 (Graphite nanofiber) was used as a catalyst support. Carbon nanofiber was oxidized to (CNF-O) with 5% and 65 % concentration of nitric acid (HNO 3 ). The CNF activated with 5% HNO 3 produced higher surface area which is 155 m 2 /g. The catalyst was characterized by X-ray Diffraction (XRD), Fourier Transform Infra-Red (FTIR) and N 2 adsorption-desorption. The results showed that increase of HNO 3 concentration reduced the surface area and porosity of the catalyst

Preparation of Mesoporous Silica-Supported Palladium Catalysts for Biofuel Upgrade

Directory of Open Access Journals (Sweden)

Ling Fei

2012-01-01

Full Text Available We report the preparation of two hydrocracking catalysts Pd/CoMoO4/silica and Pd/CNTs/CoMoO4/silica (CNTs, carbon nanotubes. The structure, morphologies, composition, and thermal stability of catalysts were studied by X-ray diffraction (XRD, scanning electron microscopy (SEM, Raman spectroscopy, transmission electron microscopy (TEM, energy-dispersive X-ray (EDX, and thermogravimetric analysis (TGA. The catalyst activity was measured in a Parr reactor with camelina fatty acid methyl esters (FAMEs as the feed. The analysis shows that the palladium nanoparticles have been incorporated onto mesoporous silica in Pd/CoMoO4/silica or on the CNTs surface in Pd/CNTs/CoMoO4/silica catalysts. The different combinations of metals and supports have selective control cracking on heavy hydrocarbons.

The utilization of hydroxyapatite-supported CaO-CeO_2 catalyst for biodiesel production

International Nuclear Information System (INIS)

Yan, Beibei; Zhang, Ying; Chen, Guanyi; Shan, Rui; Ma, Wenchao; Liu, Changye

2016-01-01

Highlights: • Hydroxyapatite derived from waste animal bones was served as the support for bimetallic CaO-CeO_2 catalyst. • The 30%CaO-CeO_2/HAP-650 catalyst exhibited excellent performance on biodiesel production. • The yield of FAME was 84.4 % after eight cycles. • Minor leaching concentrations of cerium and calcium species were detected in the product. - Abstract: The study investigated the effect of a bimetallic supported catalyst in biodiesel production. Calcined waste bone derived hydroxyapatite (HAP), a solid waste from animal, was served as the support for CaO-CeO_2 catalyst. Various characterization techniques such as FT-IR, BET, SEM-EDS, CO_2-TPD and XRD analysis were used to analyse the activity of this heterogeneous catalyst. The effect of main parameters in preparation process such as calcination temperature and active component loading on catalyst performance were discussed to obtain the optimal preparation conditions. Under the optimal reaction conditions (11 wt.% dosage of 30%CaO-CeO_2/HAP-650 catalyst and 9:1 methanol to oil molar ratio at 65 °C for 3 h) the highest biodiesel yield of 91.84% was obtained. Stability test indicated that the yield (84.4%) of fatty acid methyl ester was produced after 8 re-used cycles due to the low leaching of catalyst components. The experimental results showed that biodiesel production cost might be lowered while producing relatively high yield at the present of long life-span catalyst.

Hydrogen Temperature-Programmed Desorption (H2 TPD) of Supported Platinum Catalysts.

NARCIS (Netherlands)

Koningsberger, D.C.; Miller, J.T.; Meyers, B.L.; Modica, F.S.; Lane, G.S.; Vaarkamp, M.

1993-01-01

Hydrogen temperature-programmed desorption (TPD) of supported platinum catalysts, Pt/KLTL, Pt/H-LTL, Pt/K-MAZ, Pt/H-MAZ, Pt/-Al2O3, and Pt/SiO2, was performed after hydrogen reduction at 300, 450, or 650°C. For all catalysts, reversible desorption of chemisorbed hydrogen occurred at approximately

Synthesis and comparison of the activities of a catalyst supported on two silicate materials

Energy Technology Data Exchange (ETDEWEB)

Vieira, Eduardo G., E-mail: eduardogv5007@gmail.com [Departamento de Física e Química, Unesp-Univ Estadual Paulista, Av. Brasil, 56-Centro, Caixa Postal 31, CEP 15385-000, Ilha Solteira, São Paulo (Brazil); Silva, Rafael O.; Carmo, Devaney R. do [Departamento de Física e Química, Unesp-Univ Estadual Paulista, Av. Brasil, 56-Centro, Caixa Postal 31, CEP 15385-000, Ilha Solteira, São Paulo (Brazil); Junior, Enes F. [Departamento de Fitotecnia, Tecnologia de Alimentos e Sócio Economia, Faculdade de Engenharia de Ilha Solteira, Universidade Estadual Paulista, Ilha Solteira, São Paulo (Brazil); Dias Filho, Newton L., E-mail: nldias@unesc.net [Departamento de Física e Química, Unesp-Univ Estadual Paulista, Av. Brasil, 56-Centro, Caixa Postal 31, CEP 15385-000, Ilha Solteira, São Paulo (Brazil); Universidade do Extremo Sul Catarinense, Av. Universitaria, 1105, CP 3167, CEP 88806-000, Criciúma, SC (Brazil)

2017-04-15

The focus of this work is inspecting the synthesis and comparison of the activities of a catalyst supported on two silicate materials in the epoxidation of 1-octene. The two new catalyst materials were characterized by infrared spectroscopy, elemental analysis, solid-state {sup 29}Si and {sup 13}C nuclear magnetic resonance, scanning electronic microscope (SEM) and analysis of nitrogen. Lastly, the two new catalysts, Silsesq-TCA-[(W(CO){sub 3}I{sub 2}){sub 3}] and Silica-TCA-[W(CO){sub 3}I{sub 2}] were tested as catalysts in reactions of epoxidation of 1-octene and compared with their analogue not supported [W(CO){sub 3}I{sub 2}(thiocarbamide)]. After an extensive literature search, we verified that our work is the first that has reported the immobilization process of [W(CO){sub 3}I{sub 2}(NCCH{sub 3}){sub 2}] on silsesquioxane and silica gel functionalized with propyl-thiocarbamide groups and their applications as catalysts of reactions of catalytic epoxidation of 1-octene. - Highlights: • Immobilization of [W(CO){sub 3}I{sub 2}(NCCH{sub 3}){sub 2}] complex onto mesoporous supports. • Synthesis and characterization of new mesoporous catalysts. • The new catalysts exhibit great catalytic activity in the epoxidation of 1-octene. • Recyclable catalysts with excellent reusability and stability.

Preparation of supported heterogeneous catalysts by pulse impregnation: Application to Ru[sub 3](CO)[sub 12]/2,2[prime]-bipyridine/SiO[sub 2] catalyst

Energy Technology Data Exchange (ETDEWEB)

Haukka, M.; Pakkanen, T.A. (Univ. of Joensuu (Finland))

1994-07-01

In this paper, the authors introduce pulse impregnation, a method for preparing supported heterogeneous catalysts by successive impregnation cycles. Pulse impregnation is a method for preparing supported heterogeneous catalysts from the liquid phase. In the pulse-impregnation technique the catalyst surface is grown gradually in consecutive cycles, with each cycle consisting of separate deposition and activation steps. During the deposition step, the catalyst precursor or precursors are deposited onto the support from a suitable solvent. The actual chemically bonded catalyst phase is formed during the activation step (e.g., thermal activation). Pulse impregnation was tested in the separate deposition of 2,2[prime]-bipyridine and Ru[sub 3](CO)[sub 12] onto a silica support, and in the preparation of Ru[sub 3](CO)[sub 12]/2,2[prime]-bipyridine/SiO[sub 2] catalyst, in a column-type reactor system. Macroscopically uniform deposition was achieved with both 2,2[prime]-bipyridine and Ru[sub 3](CO)[sub 12]. Various solvent systems were used to control the amount of solute adsorbed during deposition. In the preparation of the Ru[sub 3](CO)[sub 12]/2,2[prime]-bipyridine/SiO[sub 2] catalyst, the ruthenium content increased nearly linearly with the number of preparation cycles. The effects of the preparation method on the catalyst activity was also tested in 1-hexane hydroformylation. 31 refs., 7 figs., 1 tab.

Nature of the metal-support interface in supported metal catalysts: results from x-ray absorption spectroscopy

NARCIS (Netherlands)

Koningsberger, D.C.; Gates, B.C.

1992-01-01

X-ray absorption spectra characterizing the metal-support interface in supported metal complexes and supported metal catalysts are summarized and evaluated with 29 refs. Mononuclear transition metal complexes on non-reducible metal oxide supports are bonded with metal-oxygen bonds of .apprx.2.15

The role of Ni in sulfided carbon-supported Ni-Mo hydrodesulfurization catalysts

NARCIS (Netherlands)

Bouwens, S.M.A.M.; Barthe-Zahir, N.; Beer, de V.H.J.; Prins, R.

1991-01-01

The thiophene hydrodesulfurization activities of Ni and Ni---Mo sulfide catalysts supported on activated carbon were measured at atmospheric pressure and the catalyst structures were studied by means of X-ray photoelectron spectroscopy, dynamic oxygen chemisorption, and chemical sulfur analysis. The

Full Scale Alternative Catalyst Testing for Bosch Reactor Optimization

Science.gov (United States)

Barton, Katherine; Abney, Morgan B.

2011-01-01

Current air revitalization technology onboard the International Space Station (ISS) cannot provide complete closure of the oxygen and hydrogen loops. This makes re-supply necessary, which is possible for missions in low Earth orbit (LEO) like the ISS, but unviable for long term space missions outside LEO. In comparison, Bosch technology reduces carbon dioxide with hydrogen, traditionally over a steel wool catalyst, to create water and solid carbon. The Bosch product water can then be fed to the oxygen generation assembly to produce oxygen for crew members and hydrogen necessary to reduce more carbon dioxide. Bosch technology can achieve complete oxygen loop closure, but has many undesirable factors that result in a high energy, mass, and volume system. Finding a different catalyst with an equal reaction rate at lower temperatures with less catalyst mass and longer lifespan would make a Bosch flight system more feasible. Developmental testing of alternative catalysts for the Bosch has been performed using the Horizontal Bosch Test Stand. Nickel foam, nickel shavings, and cobalt shavings were tested at 500 C and compared to the original catalyst, steel wool. This paper presents data and analysis on the performance of each catalyst tested at comparable temperatures and recycle flow rates.

Surface-reconstructed graphite nanofibers as a support for cathode catalysts of fuel cells.

Science.gov (United States)

Gan, Lin; Du, Hongda; Li, Baohua; Kang, Feiyu

2011-04-07

Graphite nanofibers (GNFs), on which surface graphite edges were reconstructed into nano-loops, were explored as a cathode catalyst support for fuel cells. The high degree of graphitization, as well as the surface-reconstructed nano-loops that possess topological defects for uniform metal deposition, resulted in an improved performance of the GNF-supported Pt catalyst.

Chemical nature of catalysts of oxide nanoparticles in environment

Indian Academy of Sciences (India)

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

Highly active Pt nanoparticles on nickel phthalocyanine functionalized graphene nanosheets for methanol electrooxidation

International Nuclear Information System (INIS)

Zhong, Jing-Ping; Fan, You-Jun; Wang, Hui; Wang, Rui-Xiang; Fan, Li-Li; Shen, Xing-Can; Shi, Zu-Jin

2013-01-01

Highlights: • A new Pt-based catalyst using TSNiPc functionalized graphene as support is reported. • Pt nanoparticles are uniformly dispersed on the functionalized graphene surface. • The Pt/TSNiPc–graphene shows excellent catalytic performance for methanol oxidation. -- Abstract: A novel electrocatalyst using nickel (II) phthalocyanine-tetrasulfonic acid tetrasodium salt (TSNiPc) functionalized graphene (TSNiPc–graphene) composite as catalyst support for Pt nanoparticles is reported. The surface morphology, composition and structure of the prepared nanocomposites as well as their electrocatalytic properties toward methanol oxidation are characterized by UV–vis absorption spectroscopy, Raman spectroscopy, thermogravimetric analysis (TGA), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electrochemical tests. Pt nanoparticles are found uniformly dispersed on the surface of TSNiPc–graphene composite, with the small particle size of about 3.1 nm. Studies of cyclic voltammetry and chronoamperometry demonstrate that the Pt/TSNiPc–graphene exhibits much higher electrocatalytic activity and stability than the Pt/graphene catalyst for methanol oxidation

Ceramic wash-coat for catalyst support

Science.gov (United States)

Kulkarni, Anand A.; Subramanian, Ramesh; Sabol, Stephen M.

2012-08-14

A wash-coat (16) for use as a support for an active catalyst species (18) and a catalytic combustor component (10) incorporating such wash-coat. The wash-coat is a solid solution of alumina or alumina-based material (Al.sub.2O.sub.3-0-3 wt % La.sub.2O.sub.3) and a further oxide exhibiting a coefficient of thermal expansion that is lower than that exhibited by alumina. The further oxide may be silicon dioxide (2-30 wt % SiO.sub.2), zirconia silicate (2-30 wt % ZrSiO.sub.4), neodymium oxide (0-4 wt %), titania (Al.sub.2O.sub.3-3-40% TiO.sub.2) or alumina-based magnesium aluminate spinel (Al.sub.2O.sub.3-25 wt % MgO) in various embodiments. The active catalyst species may be palladium and a second metal in a concentration of 10-50% of the concentration of the palladium.

Contribution to the study of the oxidation reaction of the carbon oxide in contact with catalysts issued from the decomposition of nickel hydro-aluminates at various temperatures; Contribution a l'etude de la reaction d'oxydation de l'oxyde de carbone au contact des catalyseurs issus de la decomposition a diverses temperatures des hydroaluminates de nickel

Energy Technology Data Exchange (ETDEWEB)

Samaane, Mikhail

1966-09-26

Addressing the study of the oxidation reaction of carbon oxide which produces carbon dioxide, this research thesis reports the study of this reaction in presence of catalysts (2NiO + Al{sub 2}O{sub 3}, NiAl{sub 2}O{sub 4} and NiO + NiAl{sub 2}O{sub 4}) issued from the decomposition of nickel hydro-aluminates at different temperatures. The first part describes experimental techniques and the nature of materials used in this study. The second part reports the study of the catalytic activity of the 2NiO+Al{sub 2}O{sub 3} catalyst during the oxidation of CO. Preliminary studies are also reported: structure and texture of nickel hydro-aluminate which is the raw material used to produce catalysts, activation of this compound to develop the catalytic activity in CO oxidation, chemisorption of CO, O{sub 2} and CO{sub 2} on the 2NiO+Al{sub 2}O{sub 3} solid, interaction of adsorbed gases at the solid surface, and kinetic study of the oxidation reaction. The third part reports the study of the catalytic activity in the oxidation reaction of CO of spinel catalysts (NiAl{sub 2}O{sub 4} and NiO+NiAl{sub 2}O{sub 4}) obtained by calcination of nickel hydro-aluminates at high temperature. The formation of the spinel phase, the chemisorption of CO, O{sub 2} and CO{sub 2} on NiAl{sub 2}O{sub 4}, and the kinetic of the oxidation reaction are herein studied.

Gaseous exchange reaction of deuterium between hydrogen and water on hydrophobic catalyst supporting platinum

International Nuclear Information System (INIS)

Izawa, Hirozumi; Isomura, Shohei; Nakane, Ryohei.

1979-01-01

The deuterium exchange reaction between hydrogen and water in the gas phase where the fed hydrogen gas is saturated with water vapor is studied experimentally by use of the proper hydrophobic catalysts supporting platinum. It is found that the activities of those catalysts for this reaction system are very high compared with the other known ones for the systems in which gas and liquid should coexist on catalyst surfaces, and that the apparent catalytic activity becomes larger as the amount of platinum supported on a catalyst particle increases. By analyses of the data the following informations are obtained. The exchange reaction can be expressed by a first order reversible reaction kinetics. The pore diffusion in the catalyst particles has significant effect on the overall reaction mechanisms. (author)

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

KAUST Repository

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

2015-01-01

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

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

KAUST Repository

Alotaibi, Raja

2015-07-08

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

Silica-supported, single-site titanium catalysts for olefin epoxidation. A molecular precursor strategy for control of catalyst structure.

Science.gov (United States)

Jarupatrakorn, Jonggol; Don Tilley, T

2002-07-17

A molecular precursor approach involving simple grafting procedures was used to produce site-isolated titanium-supported epoxidation catalysts of high activity and selectivity. The tris(tert-butoxy)siloxy titanium complexes Ti[OSi(O(t)Bu)(3)](4) (TiSi4), ((i)PrO)Ti[OSi(O(t)Bu)(3)](3) (TiSi3), and ((t)BuO)(3)TiOSi(O(t)Bu)(3) (TiSi) react with the hydroxyl groups of amorphous Aerosil, mesoporous MCM-41, and SBA-15 via loss of HO(t)Bu and/or HOSi(O(t)Bu)(3) and introduction of titanium species onto the silica surface. Powder X-ray diffraction, nitrogen adsorption/desorption, infrared, and diffuse reflectance ultraviolet spectroscopies were used to investigate the structures and chemical natures of the surface-bound titanium species. The titanium species exist mainly in isolated, tetrahedral coordination environments. Increasing the number of siloxide ligands in the molecular precursor decreases the amount of titanium that can be introduced this way, but also enhances the catalytic activity and selectivity for the epoxidation of cyclohexene with cumene hydroperoxide as oxidant. In addition, the high surface area mesoporous silicas (MCM-41 and SBA-15) are more effective than amorphous silica as supports for these catalysts. Supporting TiSi3 on the SBA-15 affords highly active cyclohexene epoxidation catalysts (0.25-1.77 wt % Ti loading) that provide turnover frequencies (TOFs) of 500-1500 h(-1) after 1 h (TOFs are reduced by about half after calcination). These results demonstrate that oxygen-rich siloxide complexes of titanium are useful as precursors to supported epoxidation catalysts.

Development of supported noble metal catalyst for U(VI) to U(IV) reduction

International Nuclear Information System (INIS)

Tyagi, Deepak; Varma, Salil; Bhattacharyya, K.; Tripathi, A.K.; Bharadwaj, S.R.; Jain, V.K.; Sahu, Avinash; Vincent, Tessy; Jagatap, B.N.; Wattal, P.K.

2015-01-01

Uranium-plutonium separation is an essential step in the PUREX process employed in spent nuclear fuel reprocessing. This partitioning in the PUREX process is achieved by selective reduction of Pu(IV) to Pu(III) using uranous nitrate as reductant and hydrazine as stabilizer. Currently in our Indian reprocessing plants, the requirement of uranous nitrate is met by electrolytic reduction of uranyl nitrate. This process, however, suffers from a major drawback of incomplete reduction with a maximum conversion of ~ 60%. Catalytic reduction of U(VI) to U(IV) is being considered as one of the promising alternatives to the electro-reduction process due to fast kinetics and near total conversion. Various catalysts involving noble metals like platinum (Adams catalyst, Pt/Al 2 O 3 , Pt/SiO 2 etc.) have been reported for the reduction. Sustained activity and stability of the catalyst under harsh reaction conditions are still the issues that need to be resolved. We present here the results on zirconia supported noble metal catalyst that is developed in BARC for reduction of uranyl nitrate to uranous nitrate. Supported noble metal catalysts with varying metal loadings (0.5 - 2 wt%) were prepared via support precipitation and noble metal impregnation. The green catalysts were reduced either by chemical reduction using hydrazine hydrate or by heating in hydrogen flow or combination of both the steps. These catalysts were characterized by various techniques such as, XRD, SEM, TEM, N 2 adsorption and H 2 chemisorption. Performance of these catalysts was evaluated for U(VI) to U(IV) reduction with uranyl nitrate feed using hydrazine as reductant. The results with the most active catalyst are named as 'BARC-CAT', which was developed in our lab. (author)

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

International Nuclear Information System (INIS)

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

2014-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-04-01

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

Mechanochemical synthesis of TiO2/NiFe2O4 magnetic catalysts for operation under RF field

International Nuclear Information System (INIS)

Houlding, Thomas K.; Gao, Pengzhao; Degirmenci, Volkan; Tchabanenko, Kirill; Rebrov, Evgeny V.

2015-01-01

Highlights: • Novel NiFe 2 O 4 –TiO 2 composite magnetic catalysts have been prepared by mechanochemical synthesis. • The synthesis time of 30 min provides the highest specific absorption rate (SAR) in RF heating. • Formation of NiTiO 3 phase during calcination decreases the SAR of the catalysts. • High stability of the NiFe 2 O 4 –TiO 2 catalyst was observed in a continuous amide bond synthesis under RF heating. - Abstract: Composite NiFe 2 O 4 –TiO 2 magnetic catalysts were prepared by mechanochemical synthesis from a mixture of titania supported nickel ferrite nanoparticles and P25 titania (Evonic). The former provides fast and efficient heating under radiofrequency field, while the latter serves as an active catalyst or catalyst support. The highest heating rate was observed over a catalyst prepared for a milling time of 30 min. The catalytic activity was measured over the sulfated composite catalysts in the condensation of aniline and 3-phenylbutyric acid in a stirred tank reactor and in a continuous RF heated flow reactor in the 140–170 °C range. The product yield of 47% was obtained over the sulfated P25 titania catalyst in the flow reactor

Development of the Ni/Al{sub 2}O{sub 3}/ZrO{sub 2} catalyst to steam reforming of the natural gas process; Desenvolvimento do catalisador Ni/Al2O3/ZrO2 para o processo de reforma do gas natural

Energy Technology Data Exchange (ETDEWEB)

Neiva, Laedna Souto; Ramalho, Melanea A.F.; Costa, Ana Cristina Figueiredo de Melo; Gama, Lucianna [Universidade Federal de Campina Grande (UFCG), PB (Brazil); Andrade, Heloysa M.C. [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil); Kiminami, Ruth Herta G.A. [Universidade Federal de Sao Carlos (UFSCAR), SP (Brazil)

2008-07-01

The aim of this work is to develop catalyst of the type Ni/{alpha}-Al{sub 2}O{sub 3} modified with 0.005 mol of ZrO{sub 2} and structural, morphologic and catalytic characterizations, aiming employ in the reforming process of the natural gas. The catalytic supports were obtained by synthesis method for combustion reaction according to the concepts of the propellants chemistry. The active species of the catalyst (nickel) was deposited over the support by humid impregnation method. The catalytic supports were characterized by XRD, morphologic analysis by SEM and TEM, textural analysis by BET method before and after of the impregnation with nickel and were done catalytic tests in laboratory. The catalytic supports shows structure without any secondary phase with crystallinity elevated degree and crystal size varying between 5.7 and 7.0 nm. The catalytic test shows that these catalysts promoted a conversion percentile considerable of the natural gas in syngas. (author)

Carbon nanocages: a new support material for Pt catalyst with remarkably high durability.

Science.gov (United States)

Wang, Xiao Xia; Tan, Zhe Hua; Zeng, Min; Wang, Jian Nong

2014-03-24

Low durability is the major challenge hindering the large-scale implementation of proton exchange membrane fuel cell (PEMFC) technology, and corrosion of carbon support materials of current catalysts is the main cause. Here, we describe the finding of remarkably high durability with the use of a novel support material. This material is based on hollow carbon nanocages developed with a high degree of graphitization and concurrent nitrogen doping for oxidation resistance enhancement, uniform deposition of fine Pt particles, and strong Pt-support interaction. Accelerated degradation testing shows that such designed catalyst possesses a superior electrochemical activity and long-term stability for both hydrogen oxidation and oxygen reduction relative to industry benchmarks of current catalysts. Further testing under conditions of practical fuel cell operation reveals almost no degradation over long-term cycling. Such a catalyst of high activity, particularly, high durability, opens the door for the next-generation PEMFC for "real world" application.

Carbon Nanofibers as Catalyst Support for Noble Metals

NARCIS (Netherlands)

Toebes, M.L.

2004-01-01

In the quest for new and well-defined support materials for heterogeneous catalysts we explored the potential of carbon nanofibers (CNF). CNF belongs to the by now extensive family of synthetic graphite-like carbon materials with advantageous and tunable physico-chemical properties. Aim of the work

Toluene decomposition performance and NOx by-product formation during a DBD-catalyst process.

Science.gov (United States)

Guo, Yufang; Liao, Xiaobin; Fu, Mingli; Huang, Haibao; Ye, Daiqi

2015-02-01

Characteristics of toluene decomposition and formation of nitrogen oxide (NOx) by-products were investigated in a dielectric barrier discharge (DBD) reactor with/without catalyst at room temperature and atmospheric pressure. Four kinds of metal oxides, i.e., manganese oxide (MnOx), iron oxide (FeOx), cobalt oxide (CoOx) and copper oxide (CuO), supported on Al2O3/nickel foam, were used as catalysts. It was found that introducing catalysts could improve toluene removal efficiency, promote decomposition of by-product ozone and enhance CO2 selectivity. In addition, NOx was suppressed with the decrease of specific energy density (SED) and the increase of humidity, gas flow rate and toluene concentration, or catalyst introduction. Among the four kinds of catalysts, the CuO catalyst showed the best performance in NOx suppression. The MnOx catalyst exhibited the lowest concentration of O3 and highest CO2 selectivity but the highest concentration of NOx. A possible pathway for NOx production in DBD was discussed. The contributions of oxygen active species and hydroxyl radicals are dominant in NOx suppression. Copyright © 2014. Published by Elsevier B.V.

MASS TRANSFER IN PORE STRUCTURES OF SUPPORTED CATALYSTS

Directory of Open Access Journals (Sweden)

F.R.C. Silva

1997-09-01

Full Text Available The effects of gas-solid interaction and mass transfer in fixed-bed systems of supported catalysts were analyzed for g -Al2O3 (support and Cu/g -Al2O3 (catalyst systems. Evaluations of the mass transfer coefficients in the macropores and of the diffusivity in the micropores, as formed by the crystallite agglomerates of the metallic phases, were obtained. Dynamic experiments with gaseous tracers permitted the quantification of the parameters based on models for these two pore structures. With a flow in a range of 18 cm3 s-1 to 39.98 cm3 s-1 at 45oC, 65oC and 100oC, mass transfer coefficients km =4.33x10-4 m s-1 to 7.38x10-4 m s-1 for macropore structures and diffusivities Dm =1.29x10-11 m2 s-1 to 5.35x10-11 m2 s-1 for micropore structures were estimated

Carbon Nanofiber Supported Transition-Metal Carbide Catalysts for the Hydrodeoxygenation of Guaiacol

NARCIS (Netherlands)

Jongerius, A.; Gosselink, R.W.; Dijkstra, J.; Bitter, J.H.; Bruijnincx, P.C.A.; Weckhuysen, B.M.

2013-01-01

Hydrodeoxygenation (HDO) studies over carbon nanofiber-supported (CNF) W2C and Mo2C catalysts were performed on guaiacol, a prototypical substrate to evaluate the potential of a catalyst for valorization of depolymerized lignin streams. Typical reactions were executed at 55 bar hydrogen pressure

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

International Nuclear Information System (INIS)

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

1977-01-01

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

Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

Science.gov (United States)

Mikolajczuk-Zychora, A.; Borodzinski, A.; Kedzierzawski, P.; Mierzwa, B.; Mazurkiewicz-Pawlicka, M.; Stobinski, L.; Ciecierska, E.; Zimoch, A.; Opałło, M.

2016-12-01

One of the drawbacks of low-temperature fuel cells is high price of platinum-based catalysts used for the electroreduction of oxygen at the cathode of the fuel cell. The aim of this work is to develop the palladium catalyst that will replace commonly used platinum cathode catalysts. A series of palladium catalysts for oxygen reduction reaction (ORR) were prepared and tested on the cathode of Direct Formic Acid Fuel Cell (DFAFC). Palladium nanoparticles were deposited on the carbon black (Vulcan) and on multiwall carbon nanotubes (MWCNTs) surface by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as a reducing agent. The effect of functionalization of the carbon supports on the catalysts physicochemical properties and the ORR catalytic activity on the cathode of DFAFC was studied. The supports were functionalized by treatment in nitric acid for 4 h at 80 °C. The structure of the prepared catalysts has been characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV). Hydrophilicity of the catalytic layers was determined by measuring contact angles of water droplets. The performance of the prepared catalysts has been compared with that of the commercial 20 wt.% Pt/C (Premetek) catalyst. The maximum power density obtained for the best palladium catalyst, deposited on the surface of functionalized carbon black, is the same as that for the commercial Pt/C (Premetek). Palladium is cheaper than platinum, therefore the developed cathode catalyst is promising for future applications.

Wet catalyst-support films for production of vertically aligned carbon nanotubes.

Science.gov (United States)

Alvarez, Noe T; Hamilton, Christopher E; Pint, Cary L; Orbaek, Alvin; Yao, Jun; Frosinini, Aldo L; Barron, Andrew R; Tour, James M; Hauge, Robert H

2010-07-01

A procedure for vertically aligned carbon nanotube (VA-CNT) production has been developed through liquid-phase deposition of alumoxanes (aluminum oxide hydroxides, boehmite) as a catalyst support. Through a simple spin-coating of alumoxane nanoparticles, uniform centimer-square thin film surfaces were coated and used as supports for subsequent deposition of metal catalyst. Uniform VA-CNTs are observed to grow from this film following deposition of both conventional evaporated Fe catalyst, as well as premade Fe nanoparticles drop-dried from the liquid phase. The quality and uniformity of the VA-CNTs are comparable to growth from conventional evaporated layers of Al(2)O(3). The combined use of alumoxane and Fe nanoparticles to coat surfaces represents an inexpensive and scalable approach to large-scale VA-CNT production that makes chemical vapor deposition significantly more competitive when compared to other CNT production techniques.

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.

Electrocatalytic properties of graphite nanofibers-supported platinum catalysts for direct methanol fuel cells.

Science.gov (United States)

Park, Soo-Jin; Park, Jeong-Min; Seo, Min-Kang

2009-09-01

Graphite nanofibers (GNFs) treated at various temperatures were used as carbon supports to improve the efficiency of PtRu catalysts. The electrochemical properties of the PtRu/GNFs catalysts were then investigated to evaluate their potential for application in DMFCs. The results indicated that the particle size and dispersibility of PtRu in the catalysts were changed by heat treatment, and the electrochemical activity of the catalysts was improved. Consequently, it was found that heat treatments could have an influence on the surface and structural properties of GNFs, resulting in enhancing an electrocatalytic activity of the catalysts for DMFCs.

Cobalt supported on carbon nanofibers as catalysts for the Fischer-Tropsch synthesis

NARCIS (Netherlands)

Bezemer, G.L.

2006-01-01

The Fischer-Tropsch (FT) process converts synthesis gas (H2/CO) over a heterogeneous catalyst into hydrocarbons. Generally, cobalt catalysts supported on oxidic carriers are used for the FT process, however it appears to be difficult to obtain and maintain fully reduced cobalt particles. To overcome

Carbon-supported cobalt catalyst for hydrogen generation from alkaline sodium borohydride solution

Energy Technology Data Exchange (ETDEWEB)

Xu, Dongyan; Liu, Xinmin; Cao, Changqing; Guo, Qingjie [College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Dai, Ping [College of Electromechanical Engineering, Qingdao University of Science and Technology, Qingdao 266061 (China)

2008-08-01

Low cost transition metal catalysts with high performance are attractive for the development of on-board hydrogen generation systems by catalytic hydrolysis of sodium borohydride (NaBH{sub 4}) in fuel cell fields. In this study, hydrogen production from alkaline NaBH{sub 4} via hydrolysis process over carbon-supported cobalt catalysts was studied. The catalytic activity of the supported cobalt catalyst was found to be highly dependent on the calcination temperatures. The hydrogen generation rate increases with calcination temperatures in the range of 200-400 C, but a high calcination temperature above 500 C led to markedly decreased activity. X-ray diffraction patterns reveal that the catalysts experience phase transition from amorphous Co-B to crystalline cobalt hydroxide with increase in calcination temperatures. The reaction performance is also dependent on the concentration of NaBH{sub 4}, and the hydrogen generation rate increases for lower NaBH{sub 4} concentrations and decreases after reaching a maximum at 10 wt.% of NaBH{sub 4}. (author)

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.

Electrochemical dopamine sensor based on P-doped graphene: Highly active metal-free catalyst and metal catalyst support.

Science.gov (United States)

Chu, Ke; Wang, Fan; Zhao, Xiao-Lin; Wang, Xin-Wei; Tian, Ye

2017-12-01

Heteroatom doping is an effective strategy to enhance the catalytic activity of graphene and its hybrid materials. Despite a growing interest of P-doped graphene (P-G) in energy storage/generation applications, P-G has rarely been investigated for electrochemical sensing. Herein, we reported the employment of P-G as both metal-free catalyst and metal catalyst support for electrochemical detection of dopamine (DA). As a metal-free catalyst, P-G exhibited prominent DA sensing performances due to the important role of P doping in improving the electrocatalytic activity of graphene toward DA oxidation. Furthermore, P-G could be an efficient supporting material for loading Au nanoparticles, and resulting Au/P-G hybrid showed a dramatically enhanced electrocatalytic activity and extraordinary sensing performances with a wide linear range of 0.1-180μM and a low detection limit of 0.002μM. All these results demonstrated that P-G might be a very promising electrode material for electrochemical sensor applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Practical Stannylation of Allyl Acetates Catalyzed by Nickel with Bu3 SnOMe.

Science.gov (United States)

Komeyama, Kimihiro; Itai, Yuuhei; Takaki, Ken

2016-06-27

A practical and scalable nickel-catalyzed allylic stannylation of allyl acetates with Bu3 SnOMe is described. A variety of acyclic and cyclic allyl acetates, even with base-sensitive moieties, undergoes the stannylation by using NiBr2 /4,4'-di-tert-butylbipyridine (dtbpy)/Mn catalyst system to afford highly functionalized allyl stannanes with excellent regioselectivity and yields. Furthermore, the scope of protocol is also extended by the reaction of propargyl acetates, giving rise to propargyl or allenyl stannanes. Additionally, a unique diastereoselectivity using the nickel catalyst different from the palladium was demonstrated for the stannylation of cyclic allyl acetates. In the reaction, inexpensive and stable nickel complexes, abundant reductant (Mn), and atom-economical stannyl source were used. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption and bio-sorption of nickel ions and reuse for 2-chlorophenol catalytic ozonation oxidation degradation from water

International Nuclear Information System (INIS)

Ma, Wei; Zong, Panpan; Cheng, Zihong; Wang, Baodong; Sun, Qi

2014-01-01

Highlights: • Biomass and fly ash which were widespread for adsorption of heavy metal ions. • Preparation of catalyst by saturated adsorbents for 2-chlorophenol ozone degradation. • This work demonstrated that the O 3 /catalyst process was an effective pathway. • The use of nickel ions, fly ash and sawdust to achieve the recycling utilization of resources. -- Abstract: This work explored the preparation of an effective and low-cost catalyst and investigated its catalytic capacity for 2-chlorophenol ozonation oxidation degradation in wastewater by using an ozone oxidation batch reactor. The catalyst was directly prepared by the reuse of fly ash and sawdust after saturated adsorption of nickel ions from wastewater, which was proposed as an efficient and economic approach. The obtained catalyst was characterized by TGA, BET, FTIR, XRD, and SEM, the results showed that fly ash as the basic framework has high specific surface area and the addition of sawdust as the porogen agent could improve the pore structure of the catalyst. The adsorption of nickel ions by fly ash and sawdust from aqueous solution was also investigated in this study. The results obtained from the experiments indicated that adsorption of nickel ions by fly ash and biomass sawdust could be well described by Langmuir isotherm model and pseudo second order kinetic model. The catalytic performance of catalyst was studied in terms of the effect of time, liquid–solid ratio and pH on 2-chlorophenol ozonation degradation. It was found that the catalyst could effectively improve the ozonation reaction rate at pH = 7 with a 2:1 liquid–solid ratio. The kinetic study demonstrated that the reaction followed the first order model, and the rate constant increased 267% (0.03–0.1 min −1 ) of 2-chlorophenol ozonation degradation with 5 mmol/L concentration at pH = 7.0 compared with ozonation alone

Nickel-silver composition shows promise as catalyst for hydrogen-oxygen fuel cells

Science.gov (United States)

Magerl, J. A.; Murray, J. N.

1970-01-01

Carburized 3-1 nickel-silver preparation exhibits considerable catalytic activity, although not as high as platinum black. Cost and availability factors warrant further evaluation of nickel-silver materials.

Recycling of spent hydroprocessing catalysts: EURECAT technology

Energy Technology Data Exchange (ETDEWEB)

Berrebi, G.; Dufresne, P.; Jacquier, Y. (EURECAT-European Reprocessing Catalysts, La Voulte sur Rhone (France))

1994-04-01

Disposal of spent catalyst is a growing concern for all refiners. Environmental regulations are becoming stricter and stricter and there are State recommendations to develop disposal routes which would emphasize recycling as much as possible, and processing the wastes as near as possible to the production center. In this context, EURECAT has developed a recycling process for the hydroprocessing catalysts used in the oil refineries (NiMo, CoMo, NiW on alumina or mixed alumina silica). The process starts with a regeneration of the catalyst to eliminate hydrocarbons, carbon and sulfur. After a caustic roasting, the material is leached to obtain a solution containing mainly molybdenum (or tungsten) and vanadium, and a solid containing essentially alumina, cobalt and/or nickel. Molybdenum and vanadium are separated by an ion exchange resin technique. The solid is processed in an arc furnace to separate the alumina. Nickel and cobalt are separated by conventional solvent extraction to obtain pure metal. Alumina is disposed of as an inert slag. The strength of the process lies in the combination of proven technologies applied by companies whose reliability in their respective field is well known. The aspects concerning spent catalyst handling, packaging and transport are also discussed. 13 refs., 2 figs., 2 tabs.

Process intensification by combination of activated carbon supported catalysts and alternative energy sources

OpenAIRE

Calvino Casilda, Vanesa; Pérez-Mayoral, E.

2014-01-01

[EN] Activated carbons are well known for their catalytic properties and for being used as a catalyst support in heterogeneous catalysis. Activated carbons possess most of the desired properties of a catalyst support; inertness towards unwanted reactions, stability under regeneration and reaction conditions, suitable mechanical properties, tunable surface area, porosity, and the possibility of being manufactured in different size and shape. On the other hand, the in...

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

Energy Technology Data Exchange (ETDEWEB)

Larsson, Per-Olof

1999-05-01

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

Exceptionally Stable and Efficient Solid Supported Hoveyda-Type Catalyst

Czech Academy of Sciences Publication Activity Database

Skowerski, K.; Pastva, J.; Czarnocki, S. J.; Janošcová, Jana

2015-01-01

Roč. 19, č. 7 (2015), s. 872-877 ISSN 1083-6160 Institutional support: RVO:61388955 Keywords : OLEFIN-METATHESIS CATALYSTS * RING-CLOSING METATHESIS * N-HETEROCYCLIC CARBENES Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.922, year: 2015

Potential for preparation of hot gas cleanup sorbents from spent hydroprocessing catalysts

Energy Technology Data Exchange (ETDEWEB)

Furimsky, E.; Biagini, M. [Canada Centre for Mineral and Energy Technology, Ottawa, ON (Canada). Energy Research Labs.

1996-01-01

Three spent-decoked hydroprocessing catalysts and two corresponding fresh catalysts were tested as hot gas clean-up sorbents and compared with the zinc ferrite using a simulated coal gasification gas mixture. The catalysts deposited only by coke exhibited relatively good cleaning efficiency. The catalyst deposited by coke and metals such as vanadium and nickel was less efficient. The useful life of the spent hydroprocessing catalysts may be extended if utilized as hot gas clean-up sorbents. 12 refs., 3 figs., 4 tabs.

Effect of the dispersants on Pd species and catalytic activity of supported palladium catalyst

Energy Technology Data Exchange (ETDEWEB)

Hu, Yue [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Yang, Xiaojun, E-mail: 10100201@wit.edu.cn [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Cao, Shuo, E-mail: cao23@email.sc.edu [North America R& D Center, Clariant BU Catalysts, Louisville, 40209, KY (United States); Zhou, Jie [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Wu, Yuanxin [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Han, Jinyu [School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Yan, Zhiguo [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Zheng, Mingming [Oil Crops Research Institute, Chinese Academy of Agricultural Sciences, Hubei Key Laboratory of Oilcrops Lipid Chemistry and Nutrition, Wuhan 430062 (China)

2017-04-01

Highlights: • Polyvinyl alcohol (PVA) inhibited the sintering and reduction of Pd nanoparticles. • Activity was improved for supported Pd catalysts with PVA modified method. • PVA modified method minimized the catalyst deactivation. • This work provides an insight of the regeneration strategies for Pd catalysts. - Abstract: A series of supported palladium catalysts has been prepared through the precipitation method and the reduction method, using polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP) as dispersants. The effects of the dispersants on the properties of catalysts were evaluated and the catalytic performance of the new materials was investigated for the oxidative carbonylation of phenol to diphenyl carbonate (DPC). The catalysts as prepared were also characterized by the X-ray diffraction (XRD), transmission electron microscope (TEM), Brunner-Emmet-Teller (BET) measurements and X-ray photoelectron spectroscopy (XPS) techniques. The results show that the addition of the dispersants had no effect on the crystal phase of the catalysts. However, the dispersion of Pd particles was improved when the dispersants were used. Moreover, the particle sizes of Pd nanoparticles modified by PVA were smaller than those modified by PVP. The catalysts prepared using the dispersants gave better yields of DPC than the catalysts prepared without the dispersants. The highest yield of DPC was 17.9% with the PVA-Red catalyst. The characterization results for the used catalysts showed that the Pd species in the PVA-Red catalyst remained mostly divalent and the lattice oxygen species were consumed during the reaction, which could lead to the higher catalytic activity of the PVA-Red catalyst. The experimental results confirm that PVA effectively inhibited the sintering and reduction of active Pd species in the oxidative carbonylation of phenol.

Nb effect in the nickel oxide-catalyzed low-temperature oxidative dehydrogenation of ethane

KAUST Repository

Zhu, Haibo

2012-01-01

A method for the preparation of NiO and Nb-NiO nanocomposites is developed, based on the slow oxidation of a nickel-rich Nb-Ni gel obtained in citric acid. The resulting materials have higher surface areas than those obtained by the classical evaporation method from nickel nitrate and ammonium niobium oxalate. These consist in NiO nanocrystallites (7-13 nm) associated, at Nb contents >3 at.%., with an amorphous thin layer (1-2 nm) of a niobium-rich mixed oxide with a structure similar to that of NiNb 2O 6. Unlike bulk nickel oxides, the activity of these nanooxides for low-temperature ethane oxidative dehydrogenation (ODH) has been related to their redox properties. In addition to limiting the size of NiO crystallites, the presence of the Nb-rich phase also inhibits NiO reducibility. At Nb content >5 at.%, Nb-NiO composites are thus less active for ethane ODH but more selective, indicating that the Nb-rich phase probably covers part of the unselective, non-stoichiometric, active oxygen species of NiO. This geometric effect is supported by high-resolution transmission electron microscopy observations. The close interaction between NiO and the thin Nb-rich mixed oxide layer, combined with possible restructuration of the nanocomposite under ODH conditions, leads to significant catalyst deactivation at high Nb loadings. Hence, the most efficient ODH catalysts obtained by this method are those containing 3-4 at.% Nb, which combine high activity, selectivity, and stability. The impact of the preparation method on the structural and catalytic properties of Nb-NiO nanocomposites suggests that further improvement in NiO-catalyzed ethane ODH can be expected upon optimization of the catalyst. © 2011 Elsevier Inc. All rights reserved.

The Stability of Supported Gold Catalysts

NARCIS (Netherlands)

Masoud, Nazila

2018-01-01

Gold has supreme cultural and financial value and, in form of nanoparticles smaller than 10 nm, is a unique catalyst for different industrially relevant reactions. Intriguing properties of the gold catalysts have spurred demand in the chemical industry for Au catalysts, the application of which

Magnetic Carbon Supported Palladium Nanoparticles: An Efficient and Sustainable Catalyst for Hydrogenation Reactions

Science.gov (United States)

Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; the catalyst can be used for the hydrogenation of alkenes and reduction of aryl nitro compounds.

NMR evidence of metal-support interaction in syngas conversion catalyst Co-TiO2

International Nuclear Information System (INIS)

Murty, A.N.; Seamster, M.; Thorpe, A.N.; Obermyer, R.T.; Rao, V.U.S.

1990-01-01

To examine the relation between catalytic and magnetic properties, the zero-field NMR spectra and hysteresis loops of cobalt supported on silica, alumina, magnesia, titania, and ZSM-5 with and without the promoter thoria were investigated. Cobalt was incorporated on the support by simple physical admixture of precipitated cobalt and support, and by aqueous impregnation technique. Our studies indicate that the particle sizes are consistently lower in the presence of thoria. Of all the catalysts examined, the Co/Th/TiO 2 catalyst exhibits a high saturation magnetization value---about 20% higher than pure cobalt. In addition, the NMR spectrum of the aqueous impregnation Co/TiO 2 catalyst is distinctly different from the rest. All the NMR lines are shifted to a higher frequency by about 4 MHz. These two features---enhancement of the magnetic moment of cobalt atoms and increases in the hyperfine field at the Co nucleus---clearly indicate that there occurs strong metal-support interaction between cobalt and titania support. The higher hydrocarbon yields observed by the earlier investigators with Co/TiO 2 catalysts might be related to this phenomenon

Selective production of oxygenates from CO2 hydrogenation over mesoporous silica supported Cu-Ga nanocomposite catalyst

KAUST Repository

Huang, Kuo-Wei; Hengne, Amol Mahalingappa; Bhatte, Kushal Deepak; Ould-Chikh, Samy; Saih, Youssef; Basset, Jean-Marie

2017-01-01

Carbon dioxide hydrogenation to oxygenates (methanol and dimethyl ether (DME)) was investigated over bifunctional supported copper catalysts promoted with gallium (Ga). Supported Cu-Ga nanocomposite catalysts were characterized by X-ray diffraction

Catalytic hydrodechlorination of triclosan using a new class of anion-exchange-resin supported palladium catalysts.

Science.gov (United States)

Han, Bing; Liu, Wen; Li, Jingwen; Wang, Jin; Zhao, Dongye; Xu, Rui; Lin, Zhang

2017-09-01

We prepared a new class of anion-exchange-resin supported Pd catalysts for efficient hydrodechlorination of triclosan in water. The catalysts were prepared through an initial ion-exchange uptake of PdCl 4 2- and subsequent reduction of Pd(II) to Pd(0) nanoparticles at ambient temperature. Two standard strong-base anion exchange resins (IRA-900 and IRA-958) with different matrices (polystyrene and polyacrylic) were chosen as the supports. SEM and TEM images showed that Pd(0) nanoparticles were evenly attached on the resin surface with a mean size of 3-5 nm. The resin supported Pd catalysts (Pd@IRA-900 and Pd@IRA-958) were able to facilitate rapid and complete hydrodechlorination of triclosan. At a Pd loading of 2.0 wt.%, the observed pseudo first-order rate constant (k obs ) was 1.25 ± 0.06 and 1.6 ± 0.1 L/g/min for Pd@IRA-900 and Pd@IRA-958, respectively. The catalysts were more resistant to Cl - poisoning and natural organic matter fouling than other supported-Pd catalysts. The presence of 10 mM NaCl suppressed the k obs value by 31% and 23% for Pd@IRA-900 and Pd@IRA-958, whereas the presence of humic acid at 30 mg/L as TOC lowered the rates by 28% and 27%, respectively. The better performance of Pd@IRA-958 was attributed to the polymeric matrix properties (i.e., hydrophobicity, pore size, and surface area) as well as Pd particle size. GC/MS analyses indicated that very low concentrations of chlorinated intermediates were detected in the early stage of the hydrodechlorination process, with 2-phenoxyphenol being the main byproduct. The catalysts can be repeatedly used in multiple operations without significant bleeding. The catalysts eliminate the need for calcination in preparing conventional supported catalysts, and the resin supports conveniently facilitate control of Pd loading and material properties. Copyright © 2017 Elsevier Ltd. All rights reserved.

Electrochemical evaluation of Pt-Based binary catalysts on various supports for the direct methanol fuel cell

CSIR Research Space (South Africa)

Khotseng, L

2016-01-01

Full Text Available Ru/MoO(sub2) > PtSn/TiO(sub2) > PtRu/TiO(sub2). It was also observed that catalysts supported on MWCNTs were more active than those supported on metal oxides. Furthermore, catalysts supported on MWCNTs proved to be more stable than all the other supported...

The challenges of treating high strength wastewaters: CWAO using MWNT supported ruthenium catalysts

International Nuclear Information System (INIS)

GarcIa, J.; Gomes, H.T.; Figueiredo, J.L.; Faria, J.L.; Garcia, J.; Serp, P.; Kalck, P.

2005-01-01

High strength wastewaters containing aromatic compounds are normally not efficiently treated by conventional methods, including the common biological treatment. In these cases a more sophisticated approach is necessary to attain the desired levels of purification. Catalytic wet air oxidation (CWAO) using carbon based catalysts is employed worldwide as effective pre-treatment of effluents with these characteristics. Carbon materials are preferred as active catalysts or support for preparing them due to their morphological and structural characteristics. In the last 10 years, due to a tremendous development in materials production and processing, carbon nano-structures are becoming more accessible and common widening their range of applications [1]. In this context, the scope of the present work is to illustrate a potential use of multi-walled carbon nano-tubes (MWNT) supported ruthenium catalysts for catalytic wet air oxidation of aniline polluted wastewaters. The metal was supported by incipient wetness and excess impregnation, starting from liquid solutions of three different Ru precursors. Impregnation was carried out on modified MWNT, namely on MWNT-COOH (HNO 3 modified) and MWNT-COONa (HNO 3 /Na 2 CO 3 modified). For the 1% weight Ru/MWNT catalysts, the order of activities decreased in the sequence Ru(COD)(COT)≥RuCl 3 ≥Ru(C 5 H 5 ) 2 . The conversion of aniline after 45 min of reaction was 100% for the catalyst prepared with Ru(COD)(COT). The influence of the Ru precursor, preparation method and the support surface modification was studied comparing the conversion of aniline obtained for the different prepared Ru/MWNT catalysts (Figure 1). MWNT as support material, provide a significant metal dispersion with very small Ru nanoparticles (Figure 2) being observed. This will induce an efficient surface contact between the aniline molecule and the active sites [2]. The excellent catalytic performances of Ru/MWNT are explained in terms of the high dispersion of

A surface science study of model catalysts : II metal-support interactions in Cu/SiO2 model catalysts

NARCIS (Netherlands)

Oetelaar, van den L.C.A.; Partridge, A.; Toussaint, S.L.G.; Flipse, C.F.J.; Brongersma, H.H.

1998-01-01

The thermal stability of wet-chemically prepared Cu/SiO2 model catalysts containing nanometer-sized Cu particles on silica model supports was studied upon heating in hydrogen and ultrahigh vacuum. The surface and interface phenomena that occur are determined by the metal-support interactions.

Nano carbon supported platinum catalyst interaction behavior with perfluorosulfonic acid ionomer and their interface structures

DEFF Research Database (Denmark)

Andersen, Shuang Ma

2016-01-01

behavior of Nafion ionomer on platinized carbon nano fibers (CNFs), carbon nano tubes (CNTs) and amorphous carbon (Vulcan). The interaction is affected by the catalyst surface oxygen groups as well as porosity. Comparisons between the carbon supports and platinized equivalents are carried out. It reveals......The interaction between perfluorosulfonic acid ionomer and supported platinum catalyst is essential. It directly influences platinum accessibility, stability of carbon support and platinum, proton conductivity and electron conductivity in an electrode. In this study, we compare the adsorption...... that the platinization step modifies the surface nature of the carbon supports in terms of specific surface area, crystallinity and especially porosity; therefore, ionomer adsorption over carbon is not always representative for the ionomer adsorption over carbon supported catalyst, though indicative. Moreover...

Evaluation of Pt-Ru-Ni and Pt-Sn-Ni catalysts as anodes in direct ethanol fuel cells

Energy Technology Data Exchange (ETDEWEB)

Ribadeneira, Esteban; Hoyos, Bibian A. [Escuela de Procesos y Energia, Facultad de Minas, Universidad Nacional de Colombia, Medellin (Colombia)

2008-05-15

In this study, the electrooxidation of ethanol on carbon supported Pt-Ru-Ni and Pt-Sn-Ni catalysts is electrochemically studied through cyclic voltammetry at 50 C in direct ethanol fuel cells. All electrocatalysts are prepared using the ethylene glycol-reduction process and are chemically characterized by energy-dispersive X-ray analysis (EDX). For fuel cell evaluation, electrodes are prepared by the transfer-decal method. Nickel addition to the anode improves DEFC performance. When Pt{sub 75}Ru{sub 15}Ni{sub 10}/C is used as an anode catalyst, the current density obtained in the fuel cell is greater than that of all other investigated catalysts. Tri-metallic catalytic mixtures have a higher performance relative to bi-metallic catalysts. These results are in agreement with CV results that display greater activity for PtRuNi at higher potentials. (author)

Removal of toluene by sequential adsorption-plasma oxidation: Mixed support and catalyst deactivation.

Science.gov (United States)

Qin, Caihong; Huang, Xuemin; Zhao, Junjie; Huang, Jiayu; Kang, Zhongli; Dang, Xiaoqing

2017-07-15

A sequential adsorption-plasma oxidation system was used to remove toluene from simulated dry air using γ-Al 2 O 3 , HZSM-5, a mixture of the two materials or their supported Mn-Ag catalyst as adsorbents under atmospheric pressure and room temperature. After 120min of plasma oxidation, γ-Al 2 O 3 had a better carbon balance (∼75%) than HZSM-5, but the CO 2 yield of γ-Al 2 O 3 was only ∼50%; and there was some desorption of toluene when γ-Al 2 O 3 was used. When a mixture of HZSM-5 and γ-Al 2 O 3 with a mass ratio of 1/2 was used, the carbon balance was up to 90% and 82% of this was CO 2 . The adsorption performance and electric discharge characteristics of the mixed supports were tested in order to rationalize this high CO x yield. After seven cycles of sequential adsorption-plasma oxidation, support and Mn-Ag catalyst deactivation occurred. The support and catalyst were characterized before and after deactivation by SEM, a BET method, XRD, XPS and GC-MS in order to probe the mechanism of their deactivation. 97.6% of the deactivated supports and 76% of the deactivated catalysts could be recovered by O 2 temperature-programmed oxidation. Copyright © 2017 Elsevier B.V. All rights reserved.

Catalytic CO Oxidation over Au Nanoparticles Loaded Nanoporous Nickel Phosphate Composite

Directory of Open Access Journals (Sweden)

Xiaonan Leng

2015-01-01

Full Text Available Au/nickel phosphate-5 (Au/VSB-5 composite with the noble metal loading amount of 1.43 wt.% is prepared by using microporous VSB-5 nanocrystals as the support. Carbon monoxide (CO oxidation reaction is carried out over the sample with several catalytic cycles. Complete conversion of CO is achieved at 238°C over the catalyst at the first catalytic cycle. The catalytic activity improved greatly at the second cycle with the complete conversion fulfilled at 198°C and preserved for the other cycles. A series of experiments such as X-ray diffraction (XRD, high resolution transmission electron microscopy (HRTEM, ultraviolet-visible (UV-vis spectroscopy, and X-ray photoelectron spectroscopy (XPS are carried out to characterize the catalysts before and after the reaction to study the factors influencing this promotion at the second cycle.

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.)

Physicochemical investigations of carbon nanofiber supported Cu/ZrO{sub 2} catalyst

Energy Technology Data Exchange (ETDEWEB)

Din, Israf Ud, E-mail: drisraf@yahoo.com, E-mail: maizats@petronas.com.my; Shaharun, Maizatul S., E-mail: drisraf@yahoo.com, E-mail: maizats@petronas.com.my [Department of Fundamental and Applied Sciences, Universiti Teknologi PETRONAS (Malaysia); Subbarao, Duvvuri, E-mail: duvvuri-subbarao@petronas.com.my [Department of Chemical Engineering, Universiti Teknologi PETRONAS (Malaysia); Naeem, A., E-mail: naeeem64@yahoo.com [National Centre of Excellence in Physical Chemistry, University of Peshawar (Pakistan)

2014-10-24

Zirconia-promoted copper/carbon nanofiber catalysts (Cu‐ZrO{sub 2}/CNF) were prepared by the sequential deposition precipitation method. The Herringbone type of carbon nanofiber GNF-100 (Graphite nanofiber) was used as a catalyst support. Carbon nanofiber was oxidized to (CNF-O) with 5% and 65 % concentration of nitric acid (HNO{sub 3}). The CNF activated with 5% HNO{sub 3} produced higher surface area which is 155 m{sup 2}/g. The catalyst was characterized by X-ray Diffraction (XRD), Fourier Transform Infra-Red (FTIR) and N{sub 2} adsorption-desorption. The results showed that increase of HNO{sub 3} concentration reduced the surface area and porosity of the catalyst.

Enhanced Activity and Selectivity of Carbon Nanofiber Supported Pd Catalysts for Nitrite Reduction

KAUST Repository

Shuai, Danmeng; Choe, Jong Kwon; Shapley, John R.; Werth, Charles J.

2012-01-01

Pd-based catalyst treatment represents an emerging technology that shows promise to remove nitrate and nitrite from drinking water. In this work we use vapor-grown carbon nanofiber (CNF) supports in order to explore the effects of Pd nanoparticle size and interior versus exterior loading on nitrite reduction activity and selectivity (i.e., dinitrogen over ammonia production). Results show that nitrite reduction activity increases by 3.1-fold and selectivity decreases by 8.0-fold, with decreasing Pd nanoparticle size from 1.4 to 9.6 nm. Both activity and selectivity are not significantly influenced by Pd interior versus exterior CNF loading. Consequently, turnover frequencies (TOFs) among all CNF catalysts are similar, suggesting nitrite reduction is not sensitive to Pd location on CNFs nor Pd structure. CNF-based catalysts compare favorably to conventional Pd catalysts (i.e., Pd on activated carbon or alumina) with respect to nitrite reduction activity and selectivity, and they maintain activity over multiple reduction cycles. Hence, our results suggest new insights that an optimum Pd nanoparticle size on CNFs balances faster kinetics with lower ammonia production, that catalysts can be tailored at the nanoscale to improve catalytic performance for nitrite, and that CNFs hold promise as highly effective catalyst supports in drinking water treatment. © 2012 American Chemical Society.

Enhanced Activity and Selectivity of Carbon Nanofiber Supported Pd Catalysts for Nitrite Reduction

KAUST Repository

Shuai, Danmeng

2012-03-06

Pd-based catalyst treatment represents an emerging technology that shows promise to remove nitrate and nitrite from drinking water. In this work we use vapor-grown carbon nanofiber (CNF) supports in order to explore the effects of Pd nanoparticle size and interior versus exterior loading on nitrite reduction activity and selectivity (i.e., dinitrogen over ammonia production). Results show that nitrite reduction activity increases by 3.1-fold and selectivity decreases by 8.0-fold, with decreasing Pd nanoparticle size from 1.4 to 9.6 nm. Both activity and selectivity are not significantly influenced by Pd interior versus exterior CNF loading. Consequently, turnover frequencies (TOFs) among all CNF catalysts are similar, suggesting nitrite reduction is not sensitive to Pd location on CNFs nor Pd structure. CNF-based catalysts compare favorably to conventional Pd catalysts (i.e., Pd on activated carbon or alumina) with respect to nitrite reduction activity and selectivity, and they maintain activity over multiple reduction cycles. Hence, our results suggest new insights that an optimum Pd nanoparticle size on CNFs balances faster kinetics with lower ammonia production, that catalysts can be tailored at the nanoscale to improve catalytic performance for nitrite, and that CNFs hold promise as highly effective catalyst supports in drinking water treatment. © 2012 American Chemical Society.

A Facile Synthesis of Hollow Palladium/Copper Alloy Nanocubes Supported on N-Doped Graphene for Ethanol Electrooxidation Catalyst

Directory of Open Access Journals (Sweden)

Zhengyu Bai

2015-04-01

Full Text Available In this paper, a catalyst of hollow PdCu alloy nanocubes supported on nitrogen-doped graphene support (H-PdCu/ppy-NG is successfully synthesized using a simple one-pot template-free method. Two other catalyst materials such as solid PdCu alloy particles supported on this same nitrogen-doped graphene support (PdCu/ppy-NG and hollow PdCu alloy nanocubes supported on the reduced graphene oxide support (H-PdCu/RGO are also prepared using the similar synthesis conditions for comparison. It is found that, among these three catalyst materials, H-PdCu/ppy-NG gives the highest electrochemical active area and both the most uniformity and dispersibility of H-PdCu particles. Electrochemical tests show that the H-PdCu/ppy-NG catalyst can give the best electrocatalytic activity and stability towards the ethanol electrooxidation when compared to other two catalysts. Therefore, H-PdCu/ppy-NG should be a promising catalyst candidate for anodic ethanol oxidation in direct ethanol fuel cells.

Metal Chlorides Supported Solid Catalysts for F-C Acylations of Arenes

Institute of Scientific and Technical Information of China (English)

李阳; 刘云龙; 穆曼曼; 陈立功

2015-01-01

A series of metal chlorides supported solid catalysts were prepared by simple wet impregnation method. Their catalytic performances for Friedel-Crafts acylation of toluene with benzoyl chloride were evaluated and the excellent results were obtained over FeCl3/SiO2. These catalysts were characterized by BET, NH3-TPD and FT-IR of pyridine adsorption to clarify the structure-activity relationship. It was found that FeCl3/SiO2 has larger pore size and pore volume than other catalysts, which increased the accessibility of the catalyst. In addition, FeCl3/SiO2 ex-hibited higher molar ratio of Lewis acid sites and Brφnsted acid sites, which might be another reason for the in-crease of toluene conversion. Furthermore, the reaction parameters, including temperature, time and molar ratio, were optimized. Under the optimized conditions, 91.2%, conversion and 82.0%, selectivity were obtained. Mean-while, the generality of the catalyst was demonstrated by the acylations of alkyl substituted aromatics. Finally, the catalyst was reused for four runs with slight loss in catalytic activity, which attributed to the drain of the active component.

Based on a new support for synthesis of highly efficient palladium/hydroxyapatite catalyst for ethanol electrooxidation

International Nuclear Information System (INIS)

Cui, Qian; Chao, Shujun; Bai, Zhengyu; Yan, Huiying; Wang, Kui; Yang, Lin

2014-01-01

Based on a new support, hydroxyapatite (HAP), a facile and low–cost preparation of palladium/hydroxyapatite catalyst for ethanol electrooxidation is introduced in this paper through a solvothermal reaction without additives. HAP was employed as the catalyst support for its hydroxyl–rich surface in order to increase the stability and utilization ratio of catalyst. According to transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM) and X–ray diffraction (XRD) measurements, the as–prepared Pd nanoparticles with face–centered cubic crystal structure were evenly deposited on the surface of HAP. Cyclic voltammetry and chronoamperometry tests demonstrated that the Pd/HAP catalyst possessed a much higher current density (246 mA cm −2 ) than the Pd/C catalyst (109 mA cm −2 ) towards ethanol electrooxidation, and better stability as well. In the direct ethanol fuel cell (DEFC) test, Pd/HAP catalyst gives better performance than that with Pd/C in terms of both open-circuit voltage (OCV) and power density. These results indicate that the HAP is a better support and the catalyst developed in this study may be a better candidate for DEFCs. A possible mechanism consistent with the experimental is also proposed

XPS analysis of supported catalysts prepared in water-in-oil microemulsion system

International Nuclear Information System (INIS)

Mohd Ambar Yarmo; Wong Hoi Jin; Tan Chew Khim; Anita Ramli; Shahidan Radiman

2002-01-01

Catalysts supported on γ-alumina prepared by water-in-oil microemulsion were studied by X-ray photoelectron spectroscopy for comparison with catalysts prepared by wet impregnation. Comparable shifts to higher binding energies indicated a metal-support interaction where metal obtained via microemulsion is very small in size and highly dispersed. The positive binding energy shifts could be explained from a net unit positive charge remaining on the cluster in the photoemission final state in addition to the metallic screening from a redistribution of states within the bands. (Author)

Catalytic combustion of particulate matter Catalysts of alkaline nitrates supported on hydrous zirconium

International Nuclear Information System (INIS)

Galdeano, N.F.; Carrascull, A.L.; Ponzi, M.I.; Lick, I.D.; Ponzi, E.N.

2004-01-01

In order to explore a method to remove particulate matter, catalysts of different alkaline nitrates (Li, K and Cs) supported on hydrous zirconium were prepared by the method of incipient humidity and tested as catalysts for particulate matter combustion. The catalytic activity was determined by using the temperature programmed oxidation technique (TPO), utilizing two equipments, a thermogravimetric reactor and other of fixed bed. In the first case the particulate matter/catalyst mixture was milled carefully in a mortar (tight contact) while in the second case more realistic operative conditions were used, particulate matter/catalyst mixture was made with a spatula (loose contact). All prepared catalysts showed good activity for the particulate matter combustion. The cesium catalyst was the one that presented higher activity, decreasing the combustion temperature between 200 and 250 deg. C with respect to the combustion without catalyst. The catalyst with lithium nitrate became active at higher temperature than its melting point and the same occurred with the potassium catalyst. This did not occur for the catalyst containing cesium nitrate that melts at 407 deg. C and became active from 350 deg. C

Electrooxidation of ethanol on novel multi-walled carbon nanotube supported platinum-antimony tin oxide nanoparticle catalysts

Energy Technology Data Exchange (ETDEWEB)

Guo, Dao-Jun [School of Chemistry and Chemical Engineering, The Key Laboratory of Life-Organic Analysis, Qufu Normal University, Qufu, Shandong 273165 (China)

2011-01-15

We synthesize the new Pt based catalyst for direct ethanol fuel cells using novel multi-walled carbon nanotubes supported platinum-antimony tin oxide (Pt-ATO/MWCNT) nanoparticle as new catalyst support for the first time. The structure of Pt-ATO/MWCNT catalyst is characterized by transmission electron micrograph (TEM) and X-ray diffraction (XRD). The electrocatalytic properties of Pt-ATO/MWCNT catalyst for ethanol electrooxidation reactions are investigated by cyclic voltammetry (CV) and chronoamperometric experiments in acidic medium. The electrocatalytic activity for ethanol electrooxidation reaction shows that high carbon monoxide tolerance and good stability of Pt-ATO/MWCNT catalyst compared with Pt-SnO{sub 2}/MWCNT and commercial Pt/C are observed. These results imply that Pt-ATO/MWCNT catalyst has promising potential applications in direct alcohol fuel cells. (author)

Characterization and evaluation of Pt-Ru catalyst supported on multi-walled carbon nanotubes by electrochemical impedance

Energy Technology Data Exchange (ETDEWEB)

Ocampo, A.L.; Miranda-Hernandez, M.; Sebastian, P.J. [Centro de Investigacion en Energia-UNAM, Temixco, 62580 Morelos (Mexico); Morgado, J.; Montoya, J.A. [IMP, Eje Central Lazaro Cardenas 152, 07730 D.F. Mexico (Mexico)

2006-10-06

In this work the authors present the results of a systematic characterization and evaluation of the carbon nanotube supported Pt-Ru (Pt-Ru/CNT) for its use as methanol oxidation catalyst. Its activity was compared with that of Pt and Pt-Ru catalysts supported on Vulcan and synthesized from carbonyl precursors, and another commercial Pt-Ru catalyst. The cyclic voltammetry, CO stripping and electrochemical impedance techniques were employed to determine the electrocatalytic activity of the catalysts. The electrochemical studies were performed in 0.5M H{sub 2}SO{sub 4} containing different concentrations of methanol (0.05-1M). The results showed a noticeable influence of the catalyst support (CNT) on the performance of the catalyst for CO oxidation. The electrochemical impedance studies allowed us to separate the different steps in the methanol oxidation reaction and to control these steps or reactions by varying the applied potential and the methanol concentration. At low methanol concentration and potentials the de-hydrogenation of methanol predominated. But, at high potential and methanol concentrations, the CO oxidation predominated. These results allowed us to clearly describe at what potential and concentration ranges the bi-functional effect of Ru becomes evident. Our results indicated that the CO oxidation occurs both on Pt and Ru. Compared to other catalysts, Pt-Ru supported on carbon nanotubes showed superior catalytic activity for CO and methanol oxidation. (author)

Promising SiC support for Pd catalyst in selective hydrogenation of acetylene to ethylene

Science.gov (United States)

Guo, Zhanglong; Liu, Yuefeng; Liu, Yan; Chu, Wei

2018-06-01

In this study, SiC supported Pd nanoparticles were found to be an efficient catalyst in acetylene selective hydrogenation reaction. The ethylene selectivity can be about 20% higher than that on Pd/TiO2 catalyst at the same acetylene conversion at 90%. Moreover, Pd/SiC catalyst showed a stable catalytic life at 65 °C with 80% ethylene selectivity. With the detailed characterization using temperature-programmed reduction (H2-TPR), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 adsorption/desorption analysis, CO-chemisorption and thermo-gravimetric analysis (TGA), it was found that SiC owns a lower surface area (22.9 m2/g) and a broad distribution of meso-/macro-porosity (from 5 to 65 nm), which enhanced the mass transfer during the chemical process at high reaction rate and decreased the residence time of ethylene on catalyst surface. Importantly, SiC support has the high thermal conductivity, which favored the rapid temperature homogenization through the catalyst bed and inhabited the over-hydrogenation of acetylene. The surface electronic density of Pd on Pd/SiC catalyst was higher than that on Pd/TiO2, which could promote desorption of ethylene from surface of the catalyst. TGA results confirmed a much less coke deposition on Pd/SiC catalyst.

Characterization and Catalytic Activity of Montmorillonite K10-Supported Cobalt Catalysts

International Nuclear Information System (INIS)

Gobara, H.M.; Ghattas, M.S.; Henien, S.A.

2010-01-01

Montmorillonite K10-supported cobalt catalysts were prepared by wet impregnation method. The samples were analyzed by XRD, TPR, FTTR and BET characterization techniques. [Three phases of cobalt species were identified namely, cobalt oxide (Co 3 O 4 ), cobalt silicate (Co 2 S 1 O 4 ) and cobalt aluminate (CoAl 2 O 4 ). These species were most probably existing within the inter lamellar spaces of the meso porous montmorillonite K10 support]. The two bands observed at 1385 and 760 cm 1 were characteristic of metal species rather than the support, being mostly of Co - O bond vibration. The hysteresis loop, pore size distribution, pore volume and BET surface area were greatly affected by cobalt loading. The catalyst containing 18 wt% cobalt was the most selective sample for ethylene production from ethanol dehydration.

Evaluation of photocatalytic activities of supported catalysts on NaX zeolite or activated charcoal

Energy Technology Data Exchange (ETDEWEB)

Brites-Nóbrega, Fernanda F. de [Chemical Engineering Department, Universidade Estadual de Maringá (UEM), Av. Colombo, 5790, CEP 87020-900 Maringá, PR (Brazil); Sanitary and Environmental Engineering Department, Universidade Federal de Minas Gerais (UFMG), Av. Antônio Carlos, 6627, Campus Pampulha, Belo Horizonte, MG (Brazil); Polo, Aldino N.B.; Benedetti, Angélica M. [Chemical Engineering Department, Universidade Estadual do Oeste do Paraná (UNIOESTE), Rua da Faculdade, 645, CEP 85903-000 Toledo, PR (Brazil); Leão, Mônica M.D. [Sanitary and Environmental Engineering Department, Universidade Federal de Minas Gerais (UFMG), Av. Antônio Carlos, 6627, Campus Pampulha, Belo Horizonte, MG (Brazil); Slusarski-Santana, Veronice, E-mail: veronice.santana@unioeste.br [Chemical Engineering Department, Universidade Estadual do Oeste do Paraná (UNIOESTE), Rua da Faculdade, 645, CEP 85903-000 Toledo, PR (Brazil); Fernandes-Machado, Nádia R.C. [Chemical Engineering Department, Universidade Estadual de Maringá (UEM), Av. Colombo, 5790, CEP 87020-900 Maringá, PR (Brazil)

2013-12-15

Highlights: • The synergic effect between ZnO and NaX was positive, which increased its activity. • The best results were obtained at pH 3 and 9 with ZnO/NaX and at pH 3 with Nb{sub 2}O{sub 5}/AC. • High degradation and considerable mineralization were attained with 10% ZnO/NaX. • ZnO and Nb{sub 2}O{sub 5} supported on NaX and AC are promising alternatives as photocatalysts. -- Abstract: This study aimed to evaluate the photocatalytic activity of ZnO and Nb{sub 2}O{sub 5} catalysts, both supported on NaX zeolite and activated charcoal (AC). The synergistic effect between oxide and support and the influence of solution pH (3, 7 and 9) on photocatalytic degradation of reactive blue 5G (C.I. 222) were analyzed. The catalysts Nb{sub 2}O{sub 5}/NaX, Nb{sub 2}O{sub 5}/AC and ZnO/NaX, ZnO/AC with 5 and 10% (wt%) were prepared by wet impregnation. The results showed that the catalysts exhibit quite different structural and textural properties. The synergic effect between ZnO and NaX support was higher than that with the activated charcoal, showing that these catalysts were more efficient. The most photoactive catalyst was 10% ZnO/NaX which showed 100% discoloration of the dye solution at pH 3, 7 and 9 after 0.5, 5 and 2 h of irradiation, respectively. The hydrolytic nature of zeolite favored the formation of surface hydroxyl radicals, which increased the activity of the photocatalyst. Thus, catalysts supported on NaX zeolite are promising for use in photocatalysis.

Controlled metal nitrate decomposition for the preparation of supported metal Catalysts

NARCIS (Netherlands)

Wolters, M.

2010-01-01

High surface area supported metal (oxide) catalysts are essential for the production of fuels, chemicals, pharmaceuticals and the abatement of environmental pollution. Impregnation of high surface area supports, often silica or alumina, followed by drying, calcination and reduction is one of the

Understanding the Performance and Stability of Supported Ni-Co-Based Catalysts in Phenol HDO

Directory of Open Access Journals (Sweden)

Thuan M. Huynh

2016-11-01

Full Text Available Performances of bimetallic catalysts (Ni-Co supported on different acidic carriers (HZSM-5, HBeta, HY, ZrO2 and corresponding monometallic Ni catalysts in aqueous phase hydrodeoxygenation of phenol were compared in batch and continuous flow modes. The results revealed that the support acidity plays an important role in deoxygenation as it mainly controls the oxygen-removing steps in the reaction network. At the same time, sufficient hydrothermal stability of a solid catalyst is essential. Batch experiments revealed 10Ni10Co/HZSM-5 to be the best-performing catalyst in terms of conversion and cyclohexane yield. Complementary continuous runs provided more insights into the relationship between catalyst structure, efficiency and stability. After 24 h on-stream, the catalyst still reveals 100% conversion and a slight loss (from 100% to 90% in liquid hydrocarbon selectivity. The observed alloy of Co with Ni increased dispersion and stability of Ni-active sites, and combination with HZSM-5 resulted in a well-balanced ratio of metal and acid sites which promoted all necessary steps in preferred pathways. This was proved by studies of fresh and spent catalysts using various characterization techniques (N2 physisorption, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, transmission electron microscopy (TEM and infrared spectroscopy of adsorbed pyridine (pyr-IR.

Catalytic Copolymerization of Ethene and Carbon Monoxide on Nickel Complexes.

Science.gov (United States)

Domhöver, Bernd; Kläui, Wolfgang; Kremer-Aach, Andreas; Bell, Ralf; Mootz, Dietrich

1998-11-16

Can palladium be replaced by nickel? For the industrial copolymerization of carbon monoxide and ethene a palladium catalyst is used which cannot be recovered-a cheaper procedure would be desirable. The presented complex 1 is the first structurally characterized nickel compound which does not polymerize ethene but a mixture from carbon monoxide and ethene unter mild conditions to give a perfectly alternating polyketone. © 1998 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

Half-sandwich nickel(II complexes bearing 1,3-di(cycloalkylimidazol-2-ylidene ligands

Directory of Open Access Journals (Sweden)

Johnathon Yau

2015-11-01

Full Text Available Two new nickel catalysts have been prepared using a convenient procedure where nickelocene, the NHC·HBF4 salts, and [Et4N]Cl were heated in THF using microwave irradiation. The resulting [NiCl(Cp(NHC] complexes are air- and moisture stable in the solid state, and represent two new members of this valuable and practical class of nickel catalysts. The new species were fully characterised using methods including NMR spectroscopy and X-ray crystallography. When tested in model Suzuki–Miyaura cross-coupling reactions, these complexes were found to be active for the cross-coupling of aryl bromides and aryl chlorides.

Fabrication of nickel-foam-supported layered zinc-cobalt hydroxide nanoflakes for high electrochemical performance in supercapacitors.

Science.gov (United States)

Yuan, Peng; Zhang, Ning; Zhang, Dan; Liu, Tao; Chen, Limiao; Liu, Xiaohe; Ma, Renzhi; Qiu, Guanzhou

2014-10-04

Nickel foam supported Zn-Co hydroxide nanoflakes were fabricated by a facile solvothermal method. Benefited from the unique structure of Zn-Co hydroxide nanoflakes on a nickel foam substrate, the as prepared materials exhibited an excellent specific capacitance of 901 F g(-1) at 5 A g(-1) and remarkable cycling stability as electrode materials in supercapacitors.

Polymer supported organic catalysts for O2 reduction in Li-O2 batteries

International Nuclear Information System (INIS)

Weng, Wei; Barile, Christopher J.; Du, Peng; Abouimrane, Ali; Assary, Rajeev S.; Gewirth, Andrew A.; Curtiss, Larry A.; Amine, Khalil

2014-01-01

Graphical abstract: - Abstract: A novel organic catalyst has been synthesized that contains an anthraquinone moiety supported on a polymer backbone. This oxygen reduction catalyst was successfully incorporated in the cathode of Li-O 2 batteries. The addition of the anthraquinone-based catalyst improved the cycleability of the Li-O 2 battery when cycled in a tetraethylene glycol dimethyl ether electrolyte. Computational studies coupled with a wide range of analytical techniques including differential electrochemical mass spectrometry, cyclic voltammetry, electrochemical impedence spectroscopy, and X-ray diffraction were used to interrogate the Li-O 2 battery with and without the organic catalyst present. This study suggests that organic catalysts may serve as light and inexpensive alternatives to the precious metals frequently used in Li-O 2 batteries

The challenges of treating high strength wastewaters: CWAO using MWNT supported ruthenium catalysts

Energy Technology Data Exchange (ETDEWEB)

GarcIa, J.; Gomes, H.T.; Figueiredo, J.L.; Faria, J.L. [Porto Univ., Lab. de Catalise e Materiais, Dept. de Engenharia Quimica, Faculdade de Engenharia (Portugal); Garcia, J. [Madrid Univ. Complutense, Grupo de Catalisis y Operaciones de Separacion, Dept. de Ingenieria Quimica, Facultad de Ciencias (Spain); Serp, P.; Kalck, P. [Ecole Nationale Superieure des Ingenieurs en Arts Chimiques et Technologiques, Lab. de Catalyse, Chimie Fine et Polymeres, 31 - Toulouse (France)

2005-07-01

High strength wastewaters containing aromatic compounds are normally not efficiently treated by conventional methods, including the common biological treatment. In these cases a more sophisticated approach is necessary to attain the desired levels of purification. Catalytic wet air oxidation (CWAO) using carbon based catalysts is employed worldwide as effective pre-treatment of effluents with these characteristics. Carbon materials are preferred as active catalysts or support for preparing them due to their morphological and structural characteristics. In the last 10 years, due to a tremendous development in materials production and processing, carbon nano-structures are becoming more accessible and common widening their range of applications [1]. In this context, the scope of the present work is to illustrate a potential use of multi-walled carbon nano-tubes (MWNT) supported ruthenium catalysts for catalytic wet air oxidation of aniline polluted wastewaters. The metal was supported by incipient wetness and excess impregnation, starting from liquid solutions of three different Ru precursors. Impregnation was carried out on modified MWNT, namely on MWNT-COOH (HNO{sub 3} modified) and MWNT-COONa (HNO{sub 3}/Na{sub 2}CO{sub 3} modified). For the 1% weight Ru/MWNT catalysts, the order of activities decreased in the sequence Ru(COD)(COT){>=}RuCl{sub 3}{>=}Ru(C{sub 5}H{sub 5}){sub 2}. The conversion of aniline after 45 min of reaction was 100% for the catalyst prepared with Ru(COD)(COT). The influence of the Ru precursor, preparation method and the support surface modification was studied comparing the conversion of aniline obtained for the different prepared Ru/MWNT catalysts (Figure 1). MWNT as support material, provide a significant metal dispersion with very small Ru nanoparticles (Figure 2) being observed. This will induce an efficient surface contact between the aniline molecule and the active sites [2]. The excellent catalytic performances of Ru/MWNT are explained