X-ray studies of supported copper-aluminium catalysts

Structural peculiarities of the formation of copper-aluminium catalysts at copper concentrations <10 wt% and calcination temperatures of 573–1173 K have been studied.

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<10% . 573–1173°K.

     

Defect magnesium oxides containing acetate and nitrate ion fragments incorporated in the oxide structure

The results of studies on the synthesis of defect magnesium oxides by MgO hydration in salt solutions are summarized. The incorporation of oxygen-containing salt anions into the anionic hydroxide/oxide framework is described. In this case, the anion residue whose oxygen atoms belong to the oxygen framework of the oxide is incorporated in the octahedral oxygen cell of the oxide to occupy the place of a virtual magnesium cation. A portion of cationic vacancies remains free, whereas a portion is occupied by the transformed anion residue with a positive charge other than 2+. As a result, defect magnesium oxides are formed as substitutional solid solutions. The structure and charge heterogeneity of defect oxides is responsible for their high catalytic activity.     

A physico-chemical study of iron-chromium-molybdenum catalysts

In the study of the Fe_1–xCr_xMo_1·5O₆ system by X-ray, IR and Mössbauer methods the formation of solid state substitution solutions has been detected, which possess similar catalytic properties in methanol oxidation.

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, , Fe_1–xMo_1·5O₆ , .

     

Synthesis and Characterization of Fluorite-Like Ce-Zr-Y-La-O Systems

Ce-Zr-O and Ce-Zr-Y-La-O materials obtained under various conditions and at varying component ratios are characterized. At Ce/Zr ≈ 1, a tetragonal phase that can hardly be distinguished from a cubic phase by X-ray diffraction forms in the ternary system. Raising the precipitation temperature favors the formation of two-phase systems. Promoting the Ce/Zr = 0.26–0.62 materials with both yttrium and lanthanum favors the formation of a single-phase specimen, namely, a (Ce, Zr, Y, La)O₂ fluorite-like solid solution at 600°C. This structure persists up to 1150°C. The specific surface area of the (Ce, Zr, Y, La)O₂ materials is primarily determined by their calcination temperature: S_sp = 50–80 m²/g at 600°C and 0.6–0.8 m²/g at 1150° C. The specimens calcined at 600°C are mesoporous, with uniformly sized pores of mean diameter 32 ± 2 Å, and have no micropores. According to TPR data, the specimens calcined at 600°C are reduced with hydrogen in two steps that can apparently be interpreted as surface and bulk reduction. The Ce/Zr = 0.26 and 0.40 specimens calcined at 1150°C are reduced in a single step, giving rise to TPR peaks at 707 and 686°C, respectively, and their degree of reduction increases with decreasing Ce/Zr.     

On the mechanism of propylene oxidation over gallium-molybdenum oxide catalysts

The products of selective oxidation are shown to be formed via a stepwise mechanism with participation of surface allylic complexes. A successive transformation of -allyl to -allyl and further to acrolein is possible. The products of complete oxidation may be formed through surface carbonate-carboxylate complexes via either a stepwise mechanism involving the catalyst's oxygen, or a concerted mechanism with the participation of molecular oxygen.

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, . - -, . - , .

     

Studies of V?Mo?O systems with small vanadium content in acrolein oxidation

A solid solution of vanadium in MoO₃ with a solubility limit of about 3 mol.% V₂O₅ is shown to be formed. Its catalytic properties are discussed.

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MoO₃ 3 . % V₂O₅ .

     

Sorption equilibrium of methanol on new composite sorbents “CaCl<Subscript>2</Subscript>/silica gel”

This paper presents experimental data on methanol sorption on new composite sorbents which consist of mesoporous silica gels and calcium chloride confined to their pores. Sorption isobars and XRD analysis showed the formation of a solid crystalline solvate CaCl₂⋅2MeOH at low methanol uptake, while at higher uptake the formation of the CaCl₂–methanol solution occurred. The solution confined to the silica pores showed the sorption properties similar to those of the CaCl₂–methanol bulk solution. Calorimetric and isosteric analyses showed that the heat of methanol sorption depends on the methanol uptake, ranging from 38±2 kJ/mol for the solution to 81±4 kJ/mol for the solid crystalline phase CaCl₂⋅2MeOH. The above mentioned characterizations allowed the evaluation of the methanol sorption and the energy storage capacities, clearly showing that the optimal applications of these new composite sorbents are the methanol removal from gaseous mixtures, heat storage and sorption cooling driven by low temperature heat.     

Physico-chemical studies of the temperature range for the formation of anion-modified oxides

The effect of metal ions on the temperature range for the exstence of anion-modified oxides formed during the formation of Mg and Zn oxides and solid solutions of Cu, Al, Cr and Ni ions in these oxides through thermal decomposition of the respective hydroxo compounds, has been established.

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- , Mg Zn, Cu, Al, Cr, Ni .

     

Boehmite formation mechanism in precipitate ageing

Phase composition of the products of Al(III) hydroxide ageing at 473 K is shown to be independent of pH. Under these conditions boehmite is always formed whose morphological structure is determined by both the phase composition of freshly precipitated Al(III) hydroxides and the pH of their ageing. A possibility for the formation of needlelike boehmite crystals whose width coincides with the value of b=12.3Å of its unit cell, has been shown.

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Al(III) 473 pH, . Al(III), pH . , b=12,3 Å .

     

Development of phase composition for mixed Ni?Cu chromite catalysts. Conversions under calcination

IR spectroscopic and X-ray studies of variations in the composition of Ni, Cu and (Ni+Cu) ammonium chromates under thermal treatment show that the Ni–Cr system consists of spinel and NiO, and Cu–Cr systems consist of the spinel CuCr₂O₄ only. In mixed Ni–Cu–Cr systems part of Ni- and Cu-containing components remain independent and part of them form common Ni+Cu phases.

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Ni-, Cu- (Ni+Cu)- . , Ni–Cr NiO, Cu–Cr — CuCr₂O₄. Ni–Cu–Cr Ni- Cu- , Ni+Cu .