Sorption and activation of hydrocarbons by molecular sieves

Substantial progress has been made recently in the understanding of sorption and activation of alkanes. This progress reflects the emergence of new theoretical and experimental results, leading to a more quantitative picture of the elementary steps involved in the ordering of alkanes in molecular sieves and their chemical interaction with the acid site. Conversion of n-alkanes over various zeolites is now well understood to depend mainly upon the concentration of reactants sorbed. The sorption enthalpy and entropy of these molecules are linearly related and this relationship is characteristic of a particular molecular sieve (compensation effect). The interfacial chemistry that alkanes and alkenes undergo involves ionic species only in their transition state, whereas the stable intermediates are covalently bound. This leads to a description of the chemical transformations that resemble nucleophilic and electrophilic substitutions

Liquid phase hydrogenation of crotonaldehyde over Pt/SiO2 catalysts

The dependence of the catalytic properties of Pt/SiO2 catalysts for the hydrogenation of crotonaldehyde on the hydrogen pressure, the reaction temperature, the nature of the solvent and the presence of several additives were investigated. Strong deactivation of the catalysts mainly caused by decarbonylation of crotonaldehyde and irreversible adsorption of CO was observed. The initial activity of the deactivated catalysts is regained by oxidation of the adsorbed CO to CO2 by purging with air. The selectivity to crotylalcohol increased with increasing number of turnovers per metal site. This is explained with preferential blocking of the nonselective sites on the metal crystallites by CO and by a slow surface modification of the aging catalyst with organic deposits. The overall rate and the selectivity to the saturated aldehyde are markedly enhanced by an increase in hydrogen pressure and by a decrease in reaction temperature. The addition of modifiers such as potassium acetate, triphenylphosphine and thiophene had only little influence on the activity and the selectivity of the catalysts

Infra-red studies of the surface acidity of oxides and zeolites using adsorbed probe molecular

The use of infrared spectroscopy to probe the surface acidity of oxides and molecular sieves is reviewed. The experimental requirements and the type and nature of probe molecules available are also discussed. Special emphasis is given to the criteria that have to be met to arrive at a characterization of the solid that is useful for its catalytic application

Ways of quality improving of the ceramic bricks made from Novosibirsk region raw clay materials

"Likolor" plant is leading enterprises of the Novosibirsk region for the production of ceramic facing bricks. The research is conducted on the technological aspects of this factory to ensure the stability of quality indicators for different batches of products

Al at

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Mechanistic differences between methanol and dimethyl ether in zeolite-catalyzed hydrocarbon synthesis

Water influences critically the kinetics of the autocatalytic conversion of methanol to hydrocarbons in acid zeolites. At very low conversions but otherwise typical reaction conditions, the initiation of the reaction is delayed in presence of H$_{2}$O. In absence of hydrocarbons, the main reactions are the methanol and dimethyl ether (DME) interconversion and the formation of a C$_{1}$ reactive mixture—which in turn initiates the formation of first hydrocarbons in the zeolite pores. We conclude that the dominant reactions for the formation of a reactive C$_{1}$ pool at this stage involve hydrogen transfer from both MeOH and DME to surface methoxy groups, leading to methane and formaldehyde in a 1:1 stoichiometry. While formaldehyde reacts further to other C$_{1}$ intermediates and initiates the formation of first C–C bonds, CH$_{4}$ is not reacting. The hydride transfer to methoxy groups is the rate-determining step in the initiation of the conversion of methanol and DME to hydrocarbons. Thus, CH$_{4}$ formation rates at very low conversions, i.e., in the initiation stage before autocatalysis starts, are used to gauge the formation rates of first hydrocarbons. Kinetics, in good agreement with theoretical calculations, show surprisingly that hydrogen transfer from DME to methoxy species is 10 times faster than hydrogen transfer from methanol. This difference in reactivity causes the observed faster formation of hydrocarbons in dry feeds, when the concentration of methanol is lower than in presence of water. Importantly, the kinetic analysis of CH$_{4}$ formation rates provides a unique quantitative parameter to characterize the activity of catalysts in the methanol-to-hydrocarbon process

Design and synthesis of highly active MoVTeNb-oxides for ethane oxidative dehydrogenation

Ethane oxidative dehydrogenation (ODH) is an alternative route for ethene production. Crystalline M1 phase of Mo-V mixed metal oxide is an excellent catalyst for this reaction. Here we show a hydrothermal synthesis method that generates M1 phases with high surface areas starting from poorly soluble metal oxides. Use of organic additives allows control of the concentration of metals in aqueous suspension. Reactions leading to crystalline M1 take place at 190 °C, i.e., approximately 400 °C lower than under current synthesis conditions. The evolution of solvated polyoxometalate ions and crystalline phases in the solid is monitored by spectroscopies. Catalysts prepared by this route show higher ODH activity compared to conventionally prepared catalysts. The higher activity is due not only to the high specific surface area but also to the corrugated lateral termination of the M1 crystals, as seen by atomic resolution electron microscopy, exposing a high concentration of catalytically active sites