The Structure Stability of Metal Diffusion Membrane-Filters in the Processes of Hydrogen Absorption/Desorption

The evolution of a nanostructured state of palladium—lead membrane alloys during their interaction with hydrogen was studied using precision X-ray diffraction with synchrotron radiation (SR) and scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDXS). The importance of this topic is due to the need and demand for improving the performance characteristics of dense metal diffusion filters for high purity hydrogen separation processes. Palladium-based membrane filters with lead concentrations of 5 and 20 wt.% were prepared via electric arc melting from high purity metals (99.95%). The thickness of the filters was 50 μm. Hydrogenation was carried out from a gas medium at 573 K and the pressure of 16 atm. within 150 min. The focus of the study is on the structural state of diffusion filter membranes depending on the content of the palladium-alloying element—lead—and on analysis of the substructure of alloys before and 5300 h relaxation after hydrogenation is carried out. Specific features of the surface morphology and the structure of the membrane filters depending on the concentration of lead in the alloys are determined. The formation and development of deformation processes in metal systems upon the hydrogenation is shown. The establishment of peculiarities of hydrogen interaction with metals will contribute to obtaining new potentially important characteristics of membrane filters

Selective Synthesis of a Gasoline Fraction from CO and H₂ on a Co-SiO₂/ZSM-5/Al₂O₃ Catalyst

This article reports on a simple method for producing high-octane gasoline from CO and H2 on a Co-Al2O3/SiO2/HZSM-5/Al2O3 hybrid catalyst. In the selected pressure range (0.5, 1.0, and 2.0 MPa), it was found that a decrease in pressure and an increase in temperature contribute to an increase in the content of branched hydrocarbons. The optimal technological parameters of the process were determined to ensure high selectivity and productivity for C5–C10 hydrocarbons: pressure—1.0 MPa, ratio H2/CO = 2, gas space velocity—1000 h−1, temperature—250 °C. The selectivity for the gasoline fraction is 65.2%, and the ratio of branched to linear hydrocarbons (iso/n index) is 2.3. Under the specified technological conditions, an experimental batch of gasoline fraction (1000 cm3) was produced at the pilot plant during 400 h of continuous operation. The main physicochemical and operational parameters of the experimental gasoline fraction of hydrocarbons have been determined. The octane number determined by the research method according to GOST R 52947-2019 is 78.5 units

Ni/(R2O3,CaO) Nanocomposites Produced by the Exsolution of R1.5Ca0.5NiO4 Nickelates (R = Nd, Sm, Eu): Rare Earth Effect on the Catalytic Performance in the Dry Reforming and Partial Oxidation of Methane

In order to clarify the role of R2O3 in the metal-oxide catalysts derived from complex oxide precursors, a series of R1.5Ca0.5NiO4 (R = Nd, Sm, Eu) complex oxides was obtained. A significant systematic increase in the orthorhombic distortion of the R1.5Ca0.5NiO4 structure (K2NiF4 type, Cmce) from Nd to Eu correlates with a corresponding decrease in their ionic radii. A reduction of R1.5Ca0.5NiO4 in the Ar/H2 gas mixture at 800 °C causes a formation of dense agglomerates of CaO and R2O3 coated with spherical 25–30 nm particles of Ni metal. The size of metal particles and oxide agglomerates is similar in all Ni/(R2O3,CaO) composites in the study. Their morphology is rather similar to the products of redox exsolution obtained by the partial reduction of complex oxides. All obtained composites demonstrated a significant catalytic activity in the dry reforming (DRM) and partial oxidation (POM) of methane at 700–800 °C. A systematic decrease in the DRM catalytic activity of composites from Nd to Eu could be attributed to the basicity reduction of R2O3 components of the composite catalysts. The maximum CH4 conversion in POM reaction was observed for Ni/(Sm2O3,CaO), while the maximum selectivity was demonstrated by Nd2O3-based composite. The possible reasons for the observed difference are discussed

Al and Ti location in the MFI orthorhombic HZSM-5 framework. DFT calculation and neutron diffraction experiment

Abstract For the first time the neutron diffraction study of HZSM-5 zeolites with the general composition of (H1+x)[Al3+xSi4+12-xO24] × wH2O in the orthorhombic approximation (sp. gr. Pnma, z = 8) and initial silicate modules Si/Al = 12, 25, 40 was carried out. As a result, the composition was refined, the distribution of Al3+ ions over the tetrahedral sites (T sites) of the structure was found, and their content in each of them was estimated. It was found that T sites occupation in HZSM-5 structure differ depending on Si/Al, while samples with the same silicate module (Si/Al = 40) obtained under different synthesis conditions differ in the distribution of Al3+ ions over T sites of the structure. It was shown that the calculation of HZSM-5 zeolites crystal structure with substitutions in T sites performed using the VASP 5.2 program with different optimizations (atomic coordinates and unit cell parameters) can only reveal the most thermodynamically energetically favorable sites for Si4+ atoms substitution with other atoms (aluminum and titanium) without predicting their content in each site and regardless zeolite synthesis conditions and type of substituent atom. The relationship between HZSM-5 zeolites catalytic properties and silicate module (Si/Al, Si/Ti) was found and it cannot be ruled out that HZSM-5 catalytic activity is related to Ti4+ ions distribution over the tetrahedral sites of the structure. Graphical Abstrac

Features of the Phase Preferences, Long- and Short-Range Order in <i>Ln</i>₂(WO₄)₃ (<i>Ln</i> = Gd, Dy, Ho, Yb) with Their Relation to Hydration Behavior

The effect of synthesis conditions on the features of the long- and short-range order of Ln2(WO4)3 (Ln = Gd, Dy, Ho, Yb) powders synthesized via coprecipitation of salts has been studied by a complex of physico-chemical techniques including synchrotron X-ray powder diffraction, X-ray absorption spectroscopy, Raman and infrared spectroscopy, and simultaneous thermal analysis. It was found that crystallization of amorphous precursors begins at 600 °C/3 h and leads to the formation of the monoclinic structure with sp. gr. C12/c1(15) for Ln2(WO4)3 (Ln = Gd, Dy) and with sp. gr. P121/a1(14) for Ln = Yb, whereas crystallization of Ho precursor requires even higher temperature. After annealing at 1000 °C, the P121/a1(14) phase becomes the dominant phase component for all heavy lanthanoid types except for Ln = Gd. It was shown that the Ln (Ln = Dy, Ho, and Yb) tungstates with the P121/a1(14) monoclinic structure correspond to trihydrates Ln2(WO4)3·3H2O formed due to a rapid spontaneous hydration under ambient conditions. It was concluded that the proneness to hydration is due to a specific structure of the P121/a1(14) phase with large voids available to water molecules. Modifications in the local structure of Ln-O coordination shell accompanying the structure type change and hydration are monitored using EXAFS spectroscopy