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.     

Acidic Properties of Sulfated Zirconia

IR spectroscopy of adsorbed probe molecules (CO, pyridine) is used to characterize the acidic properties of sulfated zirconia derived from zirconium oxide and hydroxide. Their acidic properties are found to be similar. The strength of the Lewis and Brönsted site measured by the frequency shift of adsorbed CO is lower than that in zeolites. It is concluded that sulfated zirconia have no superacid Brönsted and Lewis sites. Brönsted sites capable of protonating pyridine vanish when calcining the catalysts at temperature above 773 K, but the strength and concentration of the Lewis acid sites (LAS) do not change.     

Isotope exchange between NO and H2O on a platinum-containing catalyst based on fiberglass

The dynamics of ¹⁸O isotope exchange between NO or H₂O and a catalyst and the dynamics of ¹⁸O label transfer from NO to H₂O have been studied under conditions of sorption-desorption equilibrium. The occurrence of a reaction of oxygen exchange between NO and water sorbed in the bulk of the catalyst was detected. This reaction occurs at platinum sites with the participation of acid sites of the glass matrix. The rate constants of the reaction of NO with platinum sites and the diffusion coefficients of water in the bulk of the glass matrix are evaluated.     

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.     

Catalysts Based on Fiberglass Supports: V. Absorption and Catalytic Properties of Palladium Catalysts Based on a Leached Silica-Fiberglass Support in the Selective Hydrogenation of an Ethylene–Acetylene Mixture

The absorption and catalytic properties of palladium catalysts (0.01% Pd) based on leached soda–silica fiberglass supports were studied in the selective hydrogenation of acetylene as the constituent of an ethylene–acetylene mixture. It was found that fiberglass catalysts exhibited much higher selectivity than traditional supported Pd catalysts. It was suggested that the high selectivity in the reaction of acetylene hydrogenation resulted from the selective absorption (diffusion) of acetylene in the bulk of fiberglass, where Pd microparticles are localized.     

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 .

     

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.

     

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.     

Acid properties and stability of operation of vanadium catalysts in benzene oxidation to phenol

Catalytic properties of V₂O₅/SiO₂ in benzene oxidation by N₂O were examined. Sodium additive was shown to affect the catalyst operation stability.

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V₂O₅/SiO₂ N₂O. .

     

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.