S. N. Vereshchagin1, N. N. Anshits1, A. N. Salanov2, O. M. Sharonova1, T. A. Vereshchagina1 and A. G. Anshits1 1Institute of Chemistry and Chemical Technology, Siberian Branch of the Russian Academy of Sciences, Ul. K. Marxa 42, Krasnoyarsk 660049 (Russia), E-mail: snv@icct.ru 2G. K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia)
Страницы: 303-308
The present paper reviews the processes of separation of microspheres from fly ash and their possible applications for the creation of catalytic supports, adsorbents and catalysts. To isolate magnetic microspheres and cenospheres of stabilized composition, the process flowsheets of concentrate separation, based on the combination of hydro- or aerodynamic and granulometric classification, followed by the separation in magnetic field of different intensity, were developed. Novel materials based on cenospheres of stabilized composition, such as mesoporous microspherical glasses (specific surface area Ssp = 3–50 m2/g), the supported iron oxide systems (Ssp = 50–200 m2/g), and zeolites are described. Spherical zeolites demonstrated good ion exchange properties of in cesium and strontium removal from the technological solutions. The catalytic properties of Fe2O3/cenosphere catalysts and magnetic microspheres in deep oxidation of methane are discussed.
N. A. Yazykov, A. D. Simonov, T. I. Mishenko, A. S. Aflyatunov, S. V. Smolin and V. N. Parmon
G. K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia), E-mail: A.D. Simonov@catalysis.nsk.su
Страницы: 321-326
The capability of combustion of solid fuels (such as the brown coal of the Kansk-Achinsk coal deposit) in the fluidized bed of an inert material in the presence of unmovable catalytic packages is investigated. This arrangement of the catalytic process is shown to allow the achievement of the same parameters of the fuel burn off and the content of toxic substances in the flue gas as in the case of fuel combustion in the fluidized bed of catalyst grains. The new arrangement of catalytic processes can be recommended for the accomplishing of some other exothermic catalytic reactions which require the maintenance of isothermal conditions.
Herman van Bekkum1 and Arie C. Besemer2 1Delft University of Technology, Julianalaan 136, 2628 BL Delft (The Netherlands) 2SCA Hygiene Products, PO Box 360, 3700 AJ Zeist (The Netherlands), E-mail: H.vanBekkum@stm.tudelft.nl
Страницы: 11-22
With an increasing population, up to 9 billion, and oil as well as gas stocks being finite, we should reconsider sustainable raw materials, as provided annually by plants and trees and covered by the collective term biomass, as chemical feedstock. Carbohydrates are the
E. J. M. Hensen, Q. Zhu, P. C. M. M. Magusin and R. A. van Santen
Schuit Institute of Catalysis, Laboratory of Inorganic Chemistry and Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600 MB, Eindhoven (The Netherlands), E-mail: e.j.m.hensen@tue.nl
Страницы: 31-36
The effect of high temperature calcination and steaming on iron-containing zeolite was studied. Iron was introduced by sublimation of FeCl3. FTIR measurements clearly show the disappearance of Broensted acid sites upon such treatments. This is attributed to a reaction between small occluded Fe oxide clusters obtained after initial low temperature calcination and the zeolite protons to give cationic Fe species compensating the negative zeolite charge. High temperature calcination and especially steaming considerably increase the catalyst activity in nitrous oxide decomposition. The two treated catalysts exhibit a higher apparent activation energy than the original sample. This high apparent activation energy is compensated by a high pre-exponential factor. In Fe/ZSM5 the activity mainly derives from small Fe oxide clusters, while upon treatment more active cationic species are generated. The kinetic parameters point to a stronger Fe–O bond for the latter case.
A. R. Cholach1, N. N. Bulgakov1 and B. E. Nieuwenhuys2 1G. K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia), E-mail: cholach@catalysis.nsk.su 2Leiden Institute of Chemistry, P. O. Box 9502, 2300 RA Leiden (The Netherlands)
Страницы: 47-54
The semi-empirical Method of Interacting Bonds was used in the present work to clarify the mechanism of the title process. Various single crystal planes of Pt, Rh, Ir, Fe, and Re were examined with respect to the stability of the adsorbed NHn species (n = 0, 1, 2, 3); to the reactivity of NHn (n = 0, 1, 2) species towards adsorbed hydrogen atoms; and to the possibility of proceeding the combination reactions between two NH or two NH2 particles resulting in the formation of gaseous H2 and N2 molecules. All the surfaces studied were found to form readily the stable NH species. The principal difference between Pt, Rh, Ir single crystal planes, on which the reaction exhibits rate oscillations, and Fe, Re surfaces, which do not show an oscillatory behaviour, is that the combination reaction of NH species can easily proceed in the former case, but this reaction is not allowed thermodynamically on the latter surfaces. This result is consistent with an earlier suggested mechanism for the oscillatory behaviour that attributes the surface wave propagation to the intermediate formation of NH species. Stable NH2 species can be formed on Re and Fe surfaces, whereas the noble metal surfaces can form weakly stable NH2 particles at the very edge of their existence region. The combination reaction between two NH2 species is endothermic in all cases.
V. V. Gorodetskii1, A. V. Matveev1, A. V. Kalinkin1 and B. E. Nieuwenhuys2 1G. K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia), E-mail: gorodetsk@catalysis.nsk.su 2Leiden Institute of Chemistry, P. O. Box 9502, 2300 RA Leiden (The Netherlands)
Страницы: 67-74
Detailed studies of the coadsorption of oxygen and carbon monoxide, hysteresis phenomena and oscillatory reaction of CO oxidation on Pd(110) and Pd tip surfaces have been carried out with the molecular beam (MB), field electron microscope (FEM), temperature programmed reaction (TPR) and X-ray photoelectron spectroscopy (XPS). It has been found that the occurrence of kinetic oscillations over Pd surfaces is associated with periodic formation and depletion of subsurface oxygen (Osub). Transient kinetic experiments show that CO does not react chemically with subsurface oxygen to form CO2 below 300 K. It has been found that CO does react with an atomic Oads/Osub state beginning at temperature ~150 K. Analysis of Pd tip surface with a local resolution of ~20 Å shows the availability of a sharp boundary between the mobile COads and Oads fronts.
L. A. Isupova, V. A. Sadykov, S. V. Tsybulya, G. S. Litvak, G. N. Kryukova, E. B. Burgina and A.V. Golovin
G. K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia), E-mail: isupova@catalysis.nsk.su
Страницы: 89-100
X-ray, TA, IRS, TEM and BET techniques were used to study the effect of mechanical treatment in a centrifugal planetary ball mill EI 2´150 and in a continuously operating vibration ball mill VCM-25 on physicochemical properties of powdered iron oxide of different prehistory, as well as on the properties of produced granulated supports and catalysts. The influence of structure-forming additives and electrolyte was discussed. The influence of the method used for introduction of the active component on the catalyst properties for complete oxidation of butane and CO was established.
I. V. Koptyug1, A. V. Kulikov2, A. A. Lysova1,2,3, V. A. Kirillov2, V. N. Parmon2 and R. Z. Sagdeev1 1International Tomography Center, Siberian Branch of the Russian Academy of Sciences, Ul. Institutskaya 3A, Novosibirsk 630090 (Russia), E-mail: koptyug@tomo.nsc.ru 2G. K. Boreskov Institute of Catalysis, Siberan Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia), 3Novosibirsk State University, Ul. Pirogova 2, Novosibirsk 630090 (Russia)
Страницы: 109-116
The NMR microimaging is used for the first time as an in situ method to study two model three-phase heterogeneous catalytic reactions with strong exothermicity. It is shown for the α-methylstyrene hydrogenation that in the course of the reaction, two domains coexist inside the catalyst grain which differ in the liquid phase content. The 2D maps of the liquid distribution in the course of this reaction are obtained. The reaction of the hydrogen peroxide decomposition at moderate activity of the catalyst and the H2O2 concentrations in the range of (0.03–3) M is shown to occur only in a thin layer near the catalyst surface. The influence of the medium inhomogeneity on the behaviour of the Belousov – Zhabotinsky chemical oscillator reaction is investigated as well.
R. A. Kozlovskiy1, V. F. Shvets1, A. V. Koustov1, L. E. Kitaev2, V. V. Yushchenko2, V. V. Kriventsov3, D. I. Kochubey3 and M. V. Tsodikov4 1D. I. Mendeleev University of Chemical Technology of Russia, Miusskaya Pl. 9, Moscow 125047 (Russia), E-mail: kra@muctr.edu.ru 2M. V. Lomonosov Moscow State University, Chemical Department, Vorobyovy Gory, Moscow 119899 (Russia), 3G. K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia), 4A. V. Topchiev Institute of Petrochemical Synthesis, the Russian Academy of Sciences, Leninskii prospect 29, Moscow 117912 (Russia)
Страницы: 123-130
Relationship of structure and surface properties of modified titanium dioxides, prepared by alkoxide method using derivatives of phosphoric acid as precursors, with their catalytic performance in the reaction of ethylene glycol ethoxylation was investigated. It was found, that such catalysts are mono-phase, nanocluster ones with anatase structure, and have uniform narrow pore distribution. Catalysts prepared using the amidophosphite precursors provide high catalytic activity due to the high surface acidity, and high selectivity of diethylene glycol formation due to the "sieve effect" and concert acid-base mechanism of ethylene oxide addition.
G. G. Kuvshinov, D. G. Kuvshinov and A. M. Glushenkov
G. K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia), E-mail: ggk@catalysis.nsk.su
Страницы: 135-140
Experimental studies were focused on the feasibility of utilization of hydrocarbons diluted with inert gases (such as associated oil gases) during the synthesis of nanofibrous carbon. The carbon yield and catalyst lifetime were studied regarding the initial reaction mixture parameters. Varying the composition of the initial gas mixture, it is possible to control textural characteristics of the resulting carbon product.
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