The kinetics of hydrogen sulfide sorption by the surface of a ferromanganese material containing in its composition a mixture of iron (II) and (III) oxides FeO × Fe2O3, takanelite (Mn, Ca) Mn4O9 × 3H2O and quartz SiO2, and which is samples of unrefined ferromanganese ore, was studied in this work. Sorption rate constant and activation energy constant values were calculated. The catalytic effect of iron (III) oxide was established, the presence of which in natural material contributes to a decrease in the H2S sorption activation energy. Based on the results of X-ray phase and chromatographic analysis methods, a chemical (redox) reaction of the conversion of hydrogen sulfide into elemental sulfur and H2O was revealed. The overall process rate is expressed in terms of the physical sorption stage and chemical transformation of the components; the influence of the rate of the third stage—reaction products desorption—on the overall rate of the process is taken into account. The limiting stage of the process is determined—a chemical reaction. The relation between the heat and the activation energy of the chemical transformation is used according to the Bronsted—Polanyi rule for catalytic processes. It was found that with an increase in the chemisorption heat, the activation energy of the chemisorption stage decreases and, as a consequence, its rate increases. The sorption process parameters were calculated—the Fe2O3 coverage degree with the initial substances and reaction products providing the maximum sorption rate, which can be a criterion for evaluating the catalytically active sites of the catalyst surface for carrying out catalytic reactions.
Rare earth elements (REEs) are valuable and strategically important in many high-technology areas, such as laser technology, pharmacy and metallurgy. The main methods of REE recovery are precipitation, extraction and sorption, in particular ion exchange using various sorbents, which allow to perform selective recovery and removal of associated components, as well as to separate rare earth metals with similar chemical properties. The paper examines recovery of ytterbium in the form of coordination compounds with Trilon B on weakly basic anion exchange resin D-403 from nitrate solutions. In order to estimate thermodynamic sorption parameters of ytterbium anionic complexes, ion exchange process was carried out from model solutions under constant ionic strength specified by NaNO3, optimal liquid to solid ratio, pH level, temperatures 298 and 343 K by variable concentrations method. Description of thermodynamic equilibrium was made using mass action law formulated for ion exchange equation and mathematically converted to linear form. Values of equilibrium constants, Gibbs free energy, enthalpy and entropy of the sorption process have been calculated. Basing on calculated values of Gibbs energy, a sorption series of complex REE ions with Trilon B was obtained over anion exchange resin D-403 from nitrate solutions at temperature 298 K. Sorption characteristics of anion exchange resin have been estimated: total capacity, limiting sorption of complex ions, total dynamic capacity and breakthrough dynamic capacity.
Chromium is an essential element in steelmaking industry. Steel slag inevitably contains some chromium and there is a risk of Cr emission from slag to the environment, however, in which form the emission of the element occurs and whether it is a hexavalent Cr is a concern. To investigate the conditions of hexavalent chromium formation in steel slags and its migration to the atmosphere, an estimation of Cr oxide's stabilities is carried out in this paper. Factsage 7.1 is applied to analyze the thermodynamic properties of Cr oxides with respect to the Cr6+ formation. An Ellingham diagram and standard Gibbs free energy change are proposed. Stability diagrams for BOF, EAF, and LF slag systems with various compositions are derived. Slag basicity is indicated as an influencing factor for Cr containing phase formation. Based on thermodynamic calculations Cr3+ phases are determined to be dominant for the given slags and no hexavalent Cr phases are found in the real multicomponent slag systems.
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