Localization of the copper-containing component in the pore volume of zeolite ZSM-5

The distribution of the copper-containing component in the pore volume of zeolite ZSM-5 has been investigated by H₂ and N₂ adsorption at 77 K and IR spectroscopy. Samples were synthesized by ion exchange and incipient wetness impregnation. Copper-containing clusters are mostly located on the surface of the mesopores formed by packed zeolite nanocrystallites. This causes partial blocking of the volume of microporous channels for N₂ molecules, but these channels remain accessible for H₂ molecules. It has been deduced that no considerable amount of copper located in the structural channels of the zeolite. According to IR spectroscopic data, the sorption of copper ions in the Cu/ZSM-5 catalysts takes place on extraframe-work aluminum, which forms Al-OH-Al bridges and terminal Al-OH groups, and on terminal Si-OH groups located on the zeolite crystal surface.     

Effect of modifying alumina desiccants with sulfuric acid on their physicochemical properties

In the production of alumina desiccants by extrusion, the introduction of sulfuric acid at the stage of preparing a mouldable paste based on hydroxides containing bayerite or pseudoboehmite increases the sorption capacity of the product. This effect is most pronounced for the pseudoboehmite-based materials. The dynamic capacity of these desiccants increases to the level characteristic of the bayerite-containing hydroxide (>5 g H₂O/100 cm³) for a dew point of ?40°C and a contact time of 1.5 s), and their static capacity exceeds this value (increasing from 21.13 to 23.1 g H₂O/100 cm³). This procedure changes the phase composition and textural characteristics of the pseudoboehmite-based desiccants and increases Brønsted acidity and generates strong Lewis acid sites on the surface of all oxides. The dynamic capacity of desiccants with similar textural characteristics depends on the acid-base properties of their surface.     

ESR measurements of concentration for strong surface acceptor centers on zeolites and Al2O3 using nitroxide radical TEMPON

A method to measure concentrations of strong surface acceptor centers on aluminosilicate catalysts by their titration with a solution of TEMPON (2,2,6,6-tetramethyl-4-oxypiperidine-1-oxyl) is suggested. The concentration of these centers corresponds to that of CO test molecules for the strongest acceptor centers (_CO 2210 cm^–1) obtained using IR spectroscopy. It is shown that for ZSM-5 zeolites most of these centers are localized on their external surface.

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. - - CO (_CO 2210 cm^–1). , ZSM-5 .

     

Selective oxidation of hydrocarbons into synthesis gas at short contact times: Design of monolith catalysts and main process parameters

This review summarizes the main achievements of the Boreskov Institute of Catalysis (Siberian Division, Russian Academy of Sciences) in the development of efficient and stable monolith catalysts for selective oxidation of hydrocarbons into synthesis gas at short contact times. Research in this field has included (1) design of new types of active component based on metal oxides, (2) design of new types of monolith support and development of supporting procedures for active components, and (3) optimization of process parameters for different types of fuel (natural gas, isooctane, and gasoline) and oxidant (air oxygen, including its mixtures with water and carbon dioxide), including the start-up regime. Design of active components (platinum, nickel, or their combination) supported on fluorite-like solid solutions based on cerium dioxide and rare-earth (samarium, gadolinium, and praseodymium) or zirconium cations has been aimed at separating hydrocarbon activation (on metal sites) and oxidation (on the support) and conjugating the separated steps of hydrocarbon oxidation at the metal-oxide interface. Optimization of oxygen mobility in the support lattice by varying the nature and concentration of doping cation along with optimization of hydrocarbon activation on supported metal clusters allow hydrocarbons to be completely converted into synthesis gas by selective oxidation or dry or steam reforming at contact times of a few milliseconds, ruling out undesirable carbon build-up on the catalyst surface. The development of new types of monolith support has targeted the enhancement of thermal shock resistance, including testing of supports based on thermally stable metal foils and composites (cermets). The main steps of the production of these supports have been refined, including unique technologies of blast dusting and hydrothermal treatment. The electric conductivity of these systems allows a quick startup of selective oxidation to be performed by passing electric current, and their thermal conductivity minimizes the temperature gradient arising from heat transfer in the bed. Procedures for loading monolith supports with active components have been developed, including impregnation, washcoating, or encapsulation in cermet matrices. The catalysts produced show a high efficiency and an operational stability adequate to the above tasks in the selective oxidation and steam-air autothermal reforming of natural gas (including processes under pressure), isooctane, and gasoline into synthesis gas.__________Translated from Kinetika i Kataliz, Vol. 46, No. 2, 2005, pp. 243–268.Original Russian Text Copyright © 2005 by Sadykov, Pavlova, Bunina, Alikina, Tikhov, Kuznetsova, Frolova, Lukashevich, Snegurenko, Sazonova, Kazantseva, Dyatlova, Usoltsev, Zolotarskii, Bobrova, Kuzmin, Gogin, Vostrikov, Potapova, Muzykantov, Paukshtis, Burgina, Rogov, Sobyanin, Parmon.     

Acidity of heteropoly acids with various structures and compositions studied by IR spectroscopy of the pyridinium salts

The acidity on the proton affinity scale was determined by IR spectroscopy of the pyridinium salts for nineteen heteropoly acids of nine structural types (including two with the previously unknown structure) and one isopoly acid. All heteropoly acids exhibited a high acidity at the level of CF₃SO₃H and HClO₄. H₃PW₁₂O₄₀ was the strongest acid.     

IR-spectroscopic studies of strength and concentration of acid centers on V2O5/Al2O3 catalysts

The strength of protonic sites and the concentration of acid centers in V₂O₅/Al₂O₃ catalysts have been estimated according to pyridine and ammonium adsorption.

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V₂O₅/Al₂O₃.

     

Catalysts Based on Fiberglass Supports: I. Physicochemical Properties of Silica Fiberglass Supports

The physicochemical properties and structure of supports prepared by leaching soda–silica fiberglass materials were studied using a set of physicochemical techniques (BET; IR spectroscopy; transmission electron microscopy; and ²⁹Si, ²³Na, ²⁷Al, ¹³³Cs, and ¹²⁹Xe (of adsorbed molecules) NMR spectroscopy). A matrix that corresponded in chemical composition to SiO₂was formed at high degrees of leaching; however, it was considerably different from ordinary silica gels in properties. The structure and properties of this matrix are most adequately described by the model of a pseudolayer intercalation structure, which includes alternating layers of several silicon–oxygen tetrahedrons separated by narrow (<4 Å) cavities. Considerable amounts of OH groups (5000 mol/g) are contained in these cavities, and these OH groups are different from the surface hydroxyl groups of ordinary globular silica. Although the interlayer spaces are small, comparatively bulky cations can be intercalated into them.     

Esterification of n-Butanol with Acetic Acid in the Presence of Heteropoly Acids with Different Structures and Compositions

The esterification reaction of n-butanol with acetic acid ([BuOH] : [HOAc] = 1 : 15 mol/mol; 55°C, 5% H₂O) was studied in the presence of tungsten heteropoly acids of the Keggin (H₃PW₁₂O₄₀, H₄SiW₁₂O₄₀, H₅PW₁₁TiO₄₀, H₅PW₁₁ZrO₄₀, and H₃PW₁₁ThO₃₉) and Dawson structure (-H₆P₂W₁₈O₆₂, H₆P₂W₂₁O₇₁(H₂O)₃, H₆As₂W₂₁O₆₉(H₂O), and H₂₁B₃W₃₉O₁₃₂). The reaction orders with respect to H₆P₂W₂₁O₇₁(H₂O)₃, H₃PW₁₂O₄₀, and H₆P₂W₁₈O₆₉are equal to 0.78, 1.00, and 0.97, respectively. It was found that the reaction rate depends on the acidity, as well as on the structure and composition of heteropoly acids. The H₂₁B₃W₃₉O₁₃₂heteropoly acid is most active, whereas the Keggin-structure heteropoly acids exhibit the lowest activities. Of the Keggin structure heteropoly acids, H₅PW₁₁ZrO₄₀exhibits the highest activity because of the presence of a Lewis acid site in its structure.     

Gas-Phase Carbonylation of Dimethoxymethane to Methyl Methoxyacetate on Solid Acids: The Effect of Acidity on the Catalytic Activity

The gas-phase carbonylation reaction of dimethoxymethane (DMM) to methyl methoxyacetate on different solid acids was studied. It was established that this reaction was accompanied by the occurrence of a side reaction of DMM disproportionation into dimethyl ether and methyl formate. It was shown that the activity of solid acids in both of the reactions depends on the strength of Brønsted acid sites according to an equation like the Brønsted–Evans–Polanyi–Semenov correlations.     

Surface Properties of Gas Chromatographic Adsorbents Based on Silochrome S-80 Modified by Transition Metal 8-Oxyquinolinates

Russian Journal of Physical Chemistry A - IR spectroscopy and gas chromatography are used to study the acid–base and adsorption properties of the surface of Silochrome S-80 modified with...