A. A. Budneva

Esterification of n-Butanol with Acetic Acid in the Presence of H3PW12O40 Supported on Mesoporous Carbon Materials

The adsorption of H3PW12O40 (HPA) from methanol solutions on mesoporous carbon supports (multiwall carbon nanotubes (CFC-3) and CFC modified with nitrogen atoms (N-CFC)) was studied. It was found that up to 10 wt % HPA was irreversibly adsorbed on the surface of CFC. This character of adsorption is indicative of the strong interaction of the adsorbate (HPA molecules) with coal surface groups (carboxylic, lactone, etc.) to form intermolecular hydrogen bonds with π-electron interactions. It was found that N-containing surface centers affected the adsorption of HPA on N-CFC. The acid and catalytic properties of HPA/CFC systems in the esterification reaction of n-butanol with acetic acid were studied ([BuOH]/[HOAc] = 1 : 15 mol/mol; 80°C). It was found that the strength of proton centers, which was determined as proton affinity, decreased upon supporting HPA. The HPA/CFC-3 systems most actively catalyzed the reaction. The catalytic activity of HPA/N-CFC depended on the nature of N-containing groups at the support surface, and it decreased with concentration of pyridine-like structures.

Adsorption of H3PW12O40 by porous carbon materials

Adsorption of H3PW12O40 from water and organic oxygen-containing solvents (AcOH, Me2CO, MeOH) by carbon mesoporous materials, viz., Sibunit and catalytic filamentous carbons (CFC), was studied. The amount of irreversibly sorbed heteropolyacid is 50—100 mg g–1 of support and decreases in the series of solvents: H2O > Me2CO > AcOH > MeOH. The adsorption capacity of CFC depends on the specific surface, total pore volume, and microstructure of the CFC fiber.

Hydrocracking of vacuum gas oil in the presence of supported nickel-tungsten catalysts

The supports containing 70% Al2O3 and 30% β zeolite (AZ-1 and AZ-2), which differed in mixing procedures, and the Ni-W/AZ-1 and Ni-W/AZ-2 catalysts were characterized using an adsorption technique, high-resolution electron microscopy, IR spectroscopy, and X-ray photoelectron spectroscopy and tested in the hydrocracking reaction of vacuum gas oil (VGO). It was found that the supports differed in texture characteristics and surface Lewis acidity at the same composition and similar concentrations of Brønsted acid sites. The formation of Ni-W-S sulfide species on the surfaces of both of the supports occurred in different manners: multilayer Ni-W-S sulfide species were formed on AZ-1 (Ssp = 220 m2/g), whereas single-layer species were mainly formed on AZ-2 (Ssp = 380 m2/g). It was found that catalysts containing multilayer Ni-W-S sulfide species, which were characterized by a higher degree of sulfidation, provided a higher yield of diesel fuel upon the hydrocracking of VGO, whereas catalysts containing single-layer Ni-W-S sulfide species were more active in the reactions of VGO hydrodesulfurization and hydrodenitration.

WO3/MO2 (M = Zr, Sn, Ti) heterogeneous acid catalysts: Synthesis, study, and use in cumene hydroperoxide decomposition

Thirty (5–40)% WO3/MO2 (M = Zr, Ti, Sn), heterogeneous acidic catalysts have been synthesized by two methods, specifically, via homogeneous acid solutions and from solutions brought to pH 9 with ammonia, both followed by calcination at 600–900°C. The catalysts have been characterized by IR spectroscopy and scanning electron microscopy, and their aqueous washings have been analyzed. Their acidity has been determined by the thermal analysis of samples containing adsorbed pyridine, and in terms of the proton affinity scale. Catalytic activities have been compared for cumene hydroperoxide (CHP) decomposition at 40°C in cumene and acetone. For all M, the catalysts are one type and contain W in strongly and weakly bound states, the latter being a polyoxometalate that can be washed off. Both tungstate phases are active in acid catalysis. Brønsted acid sites with a broad strength distribution have been found. The strongest of them are heteropolyacid protons. The catalysts 30% WO3/SnO2 and 20% WO3/ZrO2 (in acetone) and 10–20% WO3/TiO2 (in cumene) are the most active in CHP decomposition, and their activity is not related to their total acidity. Phases containing W6+ that form during the high-temperature synthesis are responsible for the high acidity, and additional protons that may appear owing to W6+ reduction can play only a minor role.

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.

Adsorption sites of an iron-aluminum catalyst for ammonia oxidation as studied by the IR spectroscopy of the adsorbed NO probe molecule

The state of surface adsorption sites in the IK-42-1 oxide catalyst for ammonia oxidation depending on catalyst preparation conditions (the nature of raw materials and the temperature of calcination) was studied in this work with the use of the diffuse reflectance IR spectroscopy of the adsorbed NO probe molecule. Hematite, which was prepared by a sulfate or chloride technology, was used as the starting raw material; Al2O3 binding agents were prepared by the reprecipitation or hydration of thermally activated gibbsite; and acetic or nitric acid was used as an electrolyte. The samples were calcined at 900–1000°C. It was found that mono- and dinitrosyl complexes with reduced coordinatively unsaturated Fe2+ cations and nitrite-nitrate complexes were formed upon the adsorption of NO on the catalyst surface (regardless of the catalyst preparation conditions). The samples differed in the amount and degree of coordinative unsaturation of adsorption sites depending on the preparation conditions. It was concluded that the most coordinatively unsaturated Fe2+ adsorption sites observed were formed on the surface of a solid solution of iron cations in aluminum oxide, which was formed in the course of catalyst preparation. It was found that an increase in the catalyst calcination temperature resulted in a decrease in the number of coordinatively unsaturated adsorption sites, which correlated with the observed decrease in the yield of NO. This correlation had the shape of a saturation curve, which can reflect the occurrence of a reaction in the diffusion mode at high degrees of conversion for the majority of catalysts.

Influence of the texture and acid-base properties of the alumina-containing support on the formation of Co(Ni)-Mo catalysts for deep hydrodesulfurization of the diesel fraction

The influence of the texture of γ-Al2O3 on the formation of Co(Ni)-Mo catalysts for hydrodesulfurization of the diesel fraction is studied. As shown by low-temperature N2 adsorption, X-ray diffraction, IR spectroscopy of adsorbed molecules, and high resolution electron microscopy (HREM), use of a support with a larger specific surface and a lower total concentration of terminal OH groups makes it possible to prepare more active catalysts. The electron density radial distribution method shows that the finely dispersed cobaltcontaining catalyst in its initial state contains CoMoO4, Al2(MoO4)3, and CoAl2O4, the last two phases being present in trace amounts. After the reaction, this catalyst contains cobalt-doped molybdenum sulfide. According to HREM data, the active phase of the cobalt-containing catalyst consists of layered sulfide association species Co1.3Mo2S3.3, which differ in composition from the bulk phase CoMo2S4. It is assumed that, out of the 1.3 cobalt atoms in Co1.3Mo2S3.3 0.3 Co occurs at the edges of the association species and 1.0 Co is intercalated into their interlayer space, and 0.7 S at the boundary between the association species and the Al2O3 phase is replaced by the corresponding amount of oxygen.