Search

This paper presents first investigations on a novel An(III), Ln(III), Cs(I) and Sr(II) co-extraction conceptual process using a CHON solvent composed of the calixarene crown-ether MAXCalix and the diglycolamide TODGA in a 1-octanol/kerosene diluent. The co-extraction is followed by a sequential stripping of (1) Cs(I) and Sr(II), (2) An(III) and (3) Ln(III).

Phenanthroline carboxamide compounds are promising for lanthanide intra-series separation. This paper presents a study on the effect of structure modification of phenanthroline carboxamides on the extraction of the whole lanthanide series. The study consists of theoretical calculations, extraction experiments of the 14 stable lanthanides, and extended X-ray absorption fine structure (EXAFS) analyses of Nd and Dy complexes. Tridentate monocarboxamides and tetradentate dicarboxamides show different trends in series extraction, although both preferentially extract the light lanthanides. The amide substituents, although not directly coordinating the metal ions, were also found to impact the distribution ratio, most probably due to a modification in the internal polarity of the molecules. This latter effect, if extrapolated to other nitrogen-based ligands such as pyridines or triazines, can be used to further fine-tune extractants for a process improvement.

The demand for rare earths is expected to keep increasing throughout the following years. Separation of lanthanides in particular is especially challenging because of their chemical similarities. Therefore, improving the separation process is essential. In this work, we present the effect of the counterion nature on the lanthanide extraction by a 1,10-phenanthroline derivative, the N-octyl-N-tolyl-1,10-phenanthroline-2-carboxamide in chloroform. Modification of the counterion yields a drastic change in selectivity, with a shift in the maximum of extraction from the light lanthanides (Pr, Nd, Sm) in the nitrate system to the heavy lanthanides (Dy, Ho) in the perchlorate system. Other salts (NaCl, NaNO2) showed a gradual increase in extraction along the whole lanthanide series or no effect (Na2SO4). This selectivity shift was explained by possible different coordination in the organic phase. The reversed behavior depending on the anion is especially interesting because a cycling extraction/back-extraction of light lanthanides in nitrate/chloride media or a cycling extraction/back-extraction of heavy lanthanides in perchlorate/nitrate media can enhance the separation factors of Nd and Dy/Ho, respectively.

This paper is an attempt to find out thorium oxide dissolution mechanism in HNO3-HF mixture. In a previous paper, several parameters effects on thorium oxide dissolution have been described, with specific focus on hydrofluoric acid effect, which can lead to an increase of the dissolution rate if present in small amount, but precipitates as ThF4 at higher content. Based on this previous study, experimental data were fitted using several dissolution models in order to find out the best one. Finally, a revisited model based on literature and considering the ThF4 formation was proposed. It describes the main steps of dissolution and is able to fit the experimental data for a wide range of solution compositions. This point is crucial since it allows considering an extrapolation of the established model to not-yet-studied conditions.

Cesium extraction from acidic media by seven dialkoxy-calix[4]arene-crown-6 compounds in several diluents was studied. 2-Nonanone was found to be a suitable diluent for cesium extraction. Nitric acid concentration variation reveals a maximum distribution ratio, whose position depends on extractant and diluent. This maximum was explained quantitatively by a competitive extraction of H+. An analytical mass-action extraction model accounting for activity effects is proposed that fits correctly the different datasets. The analysis showed a nitrate hyper-stoichiometry in alkyl ketone diluents. This effect yields efficient back-extraction at low acidity. Benzo substitution on the crown ether lowers nitric acid extraction, improves sodium separation, but also degrades potassium and rubidium separation.

Thorium oxide is poorly soluble: unlike uranium oxide, concentrated nitric acid medium is not sufficient to get quantitative dissolution. Addition of small amounts of fluoride is required to achieve thorium oxide total dissolution. The effect of several parameters on thorium oxide dissolution in order to optimize the dissolution conditions is reported in this paper. Thus the influence of solid characteristics, dissolution method, temperature and composition of dissolution medium on ThO2 dissolution rate has been studied. No complexing agents tested other than fluoride allows total dissolution. Beyond a given HF concentration a decrease of the dissolution rate is observed due to the formation of a precipitate at the solid/solution interface. It was demonstrated by XPS measurements that this precipitate is constituted of thorium fluoride (ThF4) formed during the ThO2 dissolution. The low concentration of HF required to achieve a total dissolution and the activation energy value measured tends to show a catalytic effect of HF on the dissolution process.

In steelmaking, secondary metallurgy steps are crucial for the quality of the final product. Adjusting the steel-grade composition and deoxidation of the liquid metal generate inclusions that can be harmful to downstream processes and to the product itself (occurrence of defects during rolling process). We present in this paper a numerical model to predict the kinetics of the elimination of inclusions by entrapment by the different phases present in the ladle (slag, bubbles injected in the liquid metal, top layer of gas). We show results for a 3D configuration, and a comparison with industrial data is performed.

We investigate the migration of bubbles in several flow patterns occurring within the gap between a rotating inner cylinder and a concentric fixed outer cylinder. The time-dependent evolution of the two-phase flow is predicted through three-dimensional Euler-Lagrange simulations. Lagrangian tracking of spherical bubbles is coupled with direct numerical simulation of the Navier-Stokes equations. We assume that bubbles do not influence the background flow (one-way coupling simulations). The force balance on each bubble takes into account buoyancy, added-mass, viscous drag and shear-induced lift forces. For increasing velocities of the rotating inner cylinder, the flow in the fluid gap evolves from the purely azimuthal steady Couette flow to Taylor toroidal vortices and eventually a wavy vortex flow. The migration of bubbles is highly dependent on the balance between buoyancy and centripetal forces (mostly due to the centripetal pressure gradient) directed toward the inner cylinder and the vortex cores. Depending on the rotation rate of the inner cylinder, bubbles tend to accumulate alternatively along the inner wall, inside the core of Taylor vortices or at particular locations within the wavy vortices. A stability analysis of the fixed points associated with bubble trajectories provides a clear understanding of their migration and preferential accumulation. The location of the accumulation points is parameterized by two dimensionless parameters expressing the balance of buoyancy, centripetal attraction toward the inner rotating cylinder, and entrapment in Taylor vortices. A complete phase diagram summarizing the various regimes of bubble migration is built. Several experimental conditions considered by Djéridi et al.1 are reproduced; the numerical results reveal a very good agreement with the experiments. When the rotation rate is further increased, the numerical results indicate the formation of oscillating bubble strings, as observed experimentally by Djéridi et al.2. After a transient state, bubbles collect at the crests or troughs of the wavy vortices. An analysis of the flow characteristics clearly indicates that bubbles accumulate in the low-pressure regions of the flow field.