Synthetic spinels of the system MgO-Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>

Synthetic spinels of the system MgO-Cr₂O₃-Al₂O₃-Fe₂O₃ are considered and the desirability of organizing their production for the refractory industry is demonstrated. Translated from Novye Ogneupory, No. 6, pp. 32–35, June 2008.     

Low-temperature anti-icing reagents in the Ca(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>-Mg(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>-CO(NH<Subscript>2</Subscript>)<Subscript>2</Subscript>-H<Subscript>2</Subscript>O system and their properties

The polytherms of ice melting in sections of the Ca(NO₃)₂-Mg(NO₃)₂-CO(NH₂)₂-H₂O system with different component ratios were studied in the temperature interval from 0 to −40°C. A series of nitrate and nitrate-carbonate reagents that are promising for the creation of anti-acing reagents were found, which form eutectics with ice at temperatures from −25 to −39°C. Their properties, viz., melting properties with respect to ice and corrosiveness on metals and alloys, were determined. An effective corrosion inhibitor was selected.     

Electrical conductivity of CuI-AsI<Subscript>3</Subscript>-As<Subscript>2</Subscript>Se<Subscript>3</Subscript> and CuI-SbI<Subscript>3</Subscript>-As<Subscript>2</Subscript>Se<Subscript>3</Subscript> chalcogenide films prepared by chemical deposition

The electrical conductivity of chalcogenide semiconductor films in the CuI-AsI₃-As₂Se₃ and CuI-SbI₃-As₂Se₃ systems, which have been prepared by chemical deposition from mono-n-butylamine, has been studied as a function of the temperature and film composition. It has been established that the electrical conductivity of the CuI-AsI₃-As₂Se₃ and CuI-SbI₃-As₂Se₃ films is predominantly determined by the copper iodide content. It has been demonstrated that the electrical properties of the chalcogenide glasses and the related films are characterized by the same values to within the experimental error, which is explained by the same model of dissolution of vitreous semiconductors in amines with the retention of the electrical properties of chalcogenide glasses after the deposition of films from their solutions.     

Europium(II) in glasses of the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript>-MnO-Eu<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Triply and doubly charged states of europium are revealed by ¹⁵¹Eu Mössbauer spectroscopy in the structure of glasses of the composition (mol %) 19.5Al₂O₃, 31.5SiO₂, 26.5MnO, and 22.5Eu₂O₃. The isomer shifts in the Mössbauer spectra of Eu³⁺ and Eu²⁺ ions in the structure of glasses differ from the isomer shifts in the spectra of the Eu₂O₃ and EuO compounds. This difference is explained by the fact that the electron density at ¹⁵¹Eu nuclei is affected by the manganese and aluminum atoms, which are not bound directly to the europium atoms. The broadening of the spectra of the Eu²⁺ ions in glasses is caused by the nonuniform isomer shift.     

CeO<Subscript>2</Subscript>-La<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZSM-5 sorbents for high-temperature H<Subscript>2</Subscript>S removal

Performance of CeO₂-La₂O₃/ZSM-5 sorbents for sulfur removal was examined at temperature ranging from 500 oC to 700 oC. The sulfur capacity of 5Ce5La/ZSM-5 was much bigger than that of CeO₂/ZSM-5. H₂ had a negative impact on the sulfidation; however, CO had little influence on sulfur removal. The characterization results showed that CeO₂ and La₂O₃ were well dispersed on ZSM-5 because of the intimate admixing of La₂O₃ and CeO₂, the major sulfidation products were Ce₂O₂S and La₂O₂S, the XRD and SEM results revealed that ZSM-5 structure could remain intact during preparation and sulfidation process, the H₂-TPR showed that the reducibility of CeO₂ can be remarkably enhanced by addition of La.     

Local crystallization of glasses in the La<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-GeO<Subscript>2</Subscript> system under laser irradiation

A method is proposed for local crystallization of glasses under laser irradiation. This method makes it possible to nucleate and grow microcrystals with a size distribution similar to a monodisperse distribution for several fractions of a second in any glass region chosen in advance. It is demonstrated using glasses in the La₂O₃-B₂O₃-GeO₂ system as an example that the crystallization of the stillwellite-like phase LaBGeO₅ with the composition close to the composition of the initial glass is observed in the glass under irradiation with the copper vapor laser operating in the high-speed pulse modulation mode. Strips (up to ～300 μm) produced at a specified depth from the glass surface contain extended regions consisting of uniformly distributed crystals, which have almost identical sizes, exhibit a pronounced faceting, and are identified using X-ray diffraction. The size and the number of crystals can be changed over a wide range by varying laser treatment conditions. This opens up the way to the design of new glass-ceramic materials in which the location of the crystalline phase in the glass bulk is controlled by a developer.     

Li<Subscript>2</Subscript>Cu<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> + SiO<Subscript>2</Subscript>/Ti compositions for the catalytic afterburning of diesel soot

Two methods were used to obtain a catalytically active oxide coating on the surface of titanium for the catalytic afterburning of diesel soot: plasma electrochemical formation of an oxide film on the surface of titanium and extraction pyrolytic deposition of the Li₂Cu₂(MoO₄)₃ compound. The Li₂Cu₂(MoO₄)₃/TiO₂ + SiO₂/Ti compositions synthesized by the single-step extraction pyrolytic treatment of the oxidized surface of titanium ensured a high burning rate of soot of ∼300°C. The subsequent deposition of Li₂Cu₂(MoO₄)₃ lowers the activity of the catalyst, due probably to the growth of molybdate phase crystallites and the filling of open oxide film pores. Double lithium-copper molybdate is able to reduce appreciably the concentration of CO in the oxidation products of soot. The advantages of these methods are the possibility of forming high-cohesion durable coatings on surfaces of any complexity, the simplicity of their implementation, and high productivity and low cost. The obtained results can be recommended for use in developing methods for creating composite coatings on catalytic soot filters.     

Unexpected Support Effect in Hydrotreating: Evidence of a Metallic Character for ReS<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and ReS<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> Catalysts

Abstract  

Rhenium sulfide based catalysts were prepared by the incipient wetness impregnation method over alumina and silica supports and evaluated for 4,6-dimethyldibenzothiophene hydrodesulfurization in a high-pressure stirred-tank reactor. The catalyst prepared over silica was about six times more active for hydrodesulfurization than the corresponding catalyst prepared over alumina and a NiMo/Al₂O₃ industrial reference catalyst. This surprising and positive SiO₂ support effect was explained by a metallic character of the supported sulfide, which was demonstrated using a kinetic approach of competitive hydrogenations and by XPS characterization.     

Crystal structure of new compound (Rb,K)<Subscript>2</Subscript>Cu<Subscript>3</Subscript>(P<Subscript>2</Subscript>O<Subscript>7</Subscript>)<Subscript>2</Subscript>

A new compound of (Rb,K)₂Cu₃(P₂O₇)₂ is obtained by high-temperature reactions from a mixture of RbNO₃, KNO₃, Cu(NO₃)₂, and (NH₄)₄P₂O₇. The crystal structure was solved by direct methods and refined to R ₁ = 0.056 for 5022 independent reflections. The compound belongs to a rhombic crystal system, P2₁2₁2₁, Z = 8, a = 9.9410(7) Å, b = 13.4754(6) Å, c = 18.6353 (3) Å, and R = 0.056. The basis of the structure is a complex copper-phosphate skeleton of the composition of [Cu₃(P₂O₇)₂]^2–, which can be regarded as consisting of two types of heteropolyhedral layers parallel to the (001) plane. The layers are alternated with each other, forming a frame, in the cavities of which the positions of alkali cations are located, statistically populated with K⁺ and Rb⁺ ions. Based on the refined populations of the positions of alkali cations, an exact chemical formula of the compound can be written as Rb_1.28K_0.72Cu₃(P₂O₇)₂. The compound is the most complex among those known to this day of the composition of A₂ ^IB₃ ^II(P₂O₇)₂ (A = Li, Na, K, Rb, or Cs; B = Ni, Cu, or Zn).     

Phase Equilibria in the Gd<Subscript>2</Subscript>O<Subscript>3</Subscript>-SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript> System

The phase equilibria are investigated and the phase diagram is constructed for the Gd₂O₃-SrAl₂O₄ pseudobinary join of the Gd₂O₃-SrO-Al₂O₃ ternary oxide system. One ternary compound, namely, Gd₂SrAl₂O₇, is revealed in the Gd₂O₃-SrAl₂O₄ join. It is found that this compound undergoes congruent melting.     

Phase equilibria in the Ho<Subscript>2</Subscript>O<Subscript>3</Subscript>-SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript> system

The phase formation is investigated and the phase diagram of the Ho₂O₃-SrAl₂O₄ system is constructed. A ternary compound, namely, Ho₂SrAl₂O₇, is revealed. It is established that this compound undergoes incongruent melting.     

Raman spectra and surface structure of CaO-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> glass leached in potassium hydroxide solutions

It is difficult to research on the surface structure of amorphous phase in fly ash during leaching reaction due to crystalline phase and complex structure. In the present work, in order to reveal the effects of leaching reaction on the surface structure of amorphous phase in fly ash, the modelling CaO-Fe₂O₃-Al₂O₃-SiO₂ glass was prepared by the traditional melting methods. The leaching reaction of CaO-Fe₂O₃-Al₂O₃-SiO₂ glass with 7.5 M KOH was investigated by spectroscopy, spectrophotometer and wet chemical method. The results show that the content of Q ¹, Q ², Q ³ and Q ⁴ of glass without corrosion was 4.21, 9.51, 23.03 and 52.55%, respectively, which shows that the network polymerization of glass is compact. The leaching reaction of glass can be described by the following equation: dS/dt = k/(r + S ₀). Leaching in KOH for various times induces the content of Q ⁴ and Q ¹ to be decreased, and Q ² and Q ³ increased, resulted in the depolymerization of network and the surface glass dissolved in alkaline solution to form a gel phase. In stage one of leaching reaction, the rate of iron ion leached from glass surface was slow, which resulted in the small slope of straight-line relationship of leaching curve. In the following stage, the leaching rate of iron ion increased with the prolongation of time.     

Interaction of O<Subscript>2</Subscript>, O<Subscript>3</Subscript>, and H<Subscript>2</Subscript>O<Subscript>2</Subscript> with an activated carbon

The results of the modification of AG-OV-1 activated carbon under various conditions (by atmospheric oxygen at elevated temperatures and by hydrogen peroxide or ozone) are given. The effect of the used modifier on changes in the porosity, surface state, and adsorption capacity of activated carbon is evaluated.     

Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript> xerogel support on hydrogen production by steam reforming of LNG over Ni/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript> catalyst

An Al₂O₃-ZrO₂ xerogel (AZ-SG) was prepared by a sol-gel method for use as a support for a nickel catalyst. The Ni/AZ-SG catalyst was then prepared by an impregnation method, and was applied to hydrogen production by steam reforming of LNG. A nickel catalyst supported on commercial alumina (A-C) was also prepared (Ni/A-C) for comparison. The hydroxyl-rich surface of the AZ-SG support increased the dispersion of nickel species on the support during the calcination step. The formation of a surface nickel aluminate-like phase in the Ni/AZ-SG catalyst greatly enhanced the reducibility of the Ni/AZ-SG catalyst. The ZrO₂ in the AZ-SG support increased the adsorption of steam onto the support and the subsequent spillover of steam from the support to the active nickel sites in the Ni/AZ-SG catalyst. Both the high surface area and the well-developed mesoporosity of the Ni/AZ-SG catalyst improved the gasification of adsorbed surface hydrocarbons in the reaction. In the steam reforming of LNG, the Ni/AZ-SG catalyst showed a better catalytic performance than the Ni/A-C catalyst. Moreover, the Ni/AZ-SG catalyst showed strong resistance toward catalyst deactivation.     

Photoreduction of CO<Subscript>2</Subscript> into CH<Subscript>4</Subscript> using Bi<Subscript>2</Subscript>S<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> double-layered dense films

Nano-sized bismuth sulfide (Bi₂S₃) and titanium dioxide (TiO₂) with the orthorhombic and anatase tetragonal structures, respectively, were synthesized for application as catalysts for the reduction of carbon dioxide (CO₂) to methane (CH₄). Four double-layered dense films were fabricated with different coating sequences—TiO₂ (bottom layer)/Bi₂S₃ (top layer), Bi₂S₃/TiO₂, TiO₂/Bi₂S₃: TiO₂ (1 : 1) mix, and Bi₂S₃: TiO₂ (1 : 1) mix/Bi₂S₃: TiO₂ (1 : 1) mix—and applied to the photoreduction of CO₂ to CH₄; the catalytic activity of the fabricated films was compared to that of the pure TiO₂/TiO₂ and Bi₂S₃/Bi₂S₃ doubled-layered films. The TiO₂/Bi₂S₃ double-layered film exhibited superior photocatalytic behavior, and higher CH₄ production was obtained with the TiO₂/Bi₂S₃ double-layered film than with the other films. A model of the mechanism underlying the enhanced photoactivity of the TiO₂/Bi₂S₃ double-layered film was proposed, and it was attributed in effective charge separation.