Investigation of the separation of scandium and rare earth elements from red mud by use of reversed-phase HPLC

A chromatographic method has been developed for separation and determination of scandium (Sc) and rare earth elements (REEs) in samples from a red mud (RM)-utilization process. Reversed-phase high-performance liquid chromatography (RP-HPLC) with post-column derivatization using 4-(2-pyridylazo)-resorcinol (PAR) and UV–visible detection at 520 nm was tested using different gradient elution profiles and pH values to optimize separation and recovery, primarily for Sc but also for yttrium and the individual lanthanides, from iron present in the samples. The separation was performed in less than 20 min by use of a mobile phase gradient. The concentration of -hydroxyisobutyric acid (-HIBA), as eluent, was altered from 0.06 to 0.4 mol L^–1 (pH 3.7) and 0.01 mol L^–1 sodium salt n-octane sulfonic acid (OS) was used as modifier. Very low detection limits in the nanogram range and a good resolution for Sc and REEs except for Y/Dy were achieved. Before application of the method to the red mud samples and to the corresponding bauxites, Sc and REEs were leached from red mud with 0.6 mol L^–1 HNO₃ and mostly separated, as a group, from the main elements by ion exchange/selective elution (6 mol L^–1 HNO₃) in accordance with a pilot-plant process developed in this laboratory. After evaporation of the eluent to dryness the extracted elements were re-dissolved in the mobile phase. By use of this chromatographic method Sc, which is the most expensive of the elements investigated and occurs in economically interesting concentrations in red mud, could be separated not only from co-existing Fe but also from Y/Dy, Yb, Er, Ho, Gd, Eu, Sm, Nd, Pr, Ce and La. All the elements investigated were individually recovered. Their recoveries were found to be nearly quantitative.     

Methane activation on a La0.6Sr0.4Co0.8Fe0.2O3 perovsksite; catalytic and electrocatalytic results

The catalytic and electrocatalytic behaviour of the La_0.6Sr_0.4Co_0.8Fe_0.2O₃ (LSCF) perovskite deposited on yttria stabilized zirconia (YSZ), was studied during the reaction of methane oxidation. Experiments were carried out at atmospheric pressure, and at temperatures between 600 and 900 °C. When, instead of cofeeding with methane in the gas phase, oxygen was electrochemically supplied as O²⁻, considerable changes in the methane conversion and product selectivity were observed. The non-faradaic effects (NEMCA) were also studied and compared to those observed with metal catalysts. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997     

Catalytic behavior of La0.6Sr0.4Co0.8Fe0.2O3 perovskite-type oxide thin films deposited on YSZ during the reaction of ethanol oxidation

The perovskite-type oxide La_0.6Sr_0.4Co_0.8Fe_0.2O₃ was studied as an ethanol oxidation catalyst-anode as a probable candidate for future application in Solid Oxide Fuel Cells (SOFCs). The investigation was carried out at atmospheric total pressure in a fully Yttria-Stabilized Zirconia (YSZ) continuous stirred tank reactor (C.S.T.R.) at a temperature range between 300–700 °C. Preliminary results show that La_0.6Sr_0.4Co_0.8Fe_0.2O₃ thin films deposited on the inner bottom of the one end closed YSZ tube present: a) mediocre ethanol oxidation catalytic activity at relatively low temperature values and b) thermal stability under the experimental conditions. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Catalytic and electrocatalytic oxidation of methane on palladium electrodes in a solid electrolyte cell

The catalytic oxidation of methane on polycrystalline palladium films was studied at 550-750°C and atmosheric total pressure. The reaction was studied under both open and closed-circuit. Under open circuit, and when yttria-stabilized zirconia (YSZ) was used as solid electrolyte, the technique of Solid Electrolyte Potentiometry (SEP) was used to monitor the thermodynamic activity of oxygen adsorbed on the Pd electrode during reaction. The main products were those of complete oxidation, i.e. CO₂ and H₂O. Under closed-circuit, the effect of electrochemical oxygen “pumping” to or from the catalyst was studied. Non-faradaic (NEMCA) phenomena were observed but the reaction rate enhancement factors (A) were not as large as with previously studied catalytic systems. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996.     

Thermogravimetric study of the surfactant–diethanolamine–titanium isopropoxide system behavior

Mesoporous anatase TiO₂ materials with specific surface areas between 70 and 110 m² g^?1 were prepared via sol–gel technique using surfactants oleic acid and Triton-X (TX), in the presence or absence of diethanolamine, in methanol. Surfactants like TX or oleic acid (OA), as well as a gelating and chelate agent like diethanolamine (DEA) are commonly used in TiO₂ formation from a titanium isopropoxide solution. Thermogravimetric methods were applied in order to evaluate the effect of the addition of such molecules in a precursor suspension before TiO₂ materials preparation. The in situ investigation of such systems showed that numerous interactions occur between large molecules such as TX and OA that attributed on both steric effects and hydrogen bond formation. Materials prepared through modified sol–gel technique seem to be stabilized through DEA addition in the precursor suspension.     

Enzymatic synthesis of butyryl-rutin ester in organic solvents and its cytogenetic effects in mammalian cells in culture

Enzymic acylation of a flavonoid, rutin, with trichloroethylbutyrate (TCEB) has been performed by subtilisin protease in anhydrous pyridine solution. The addition of a hydrophobic compound on rutin is expected to change the hydrophilic/hydrophobic balance of the molecule, giving new properties to this compound. This work aimed at investigating the various cytological properties of the rutin-ester and compared them with those of the native molecule. No difference in the levels of sister chromosomes exchange (SCE) between rutin and rutin-ester treated cells at doses varying from 25 to 200 μg/mL was found. On the contrary impressive difference in the induced frequency of micronuclei (MN) between rutin and rutin ester treated cells was observed, for example, at a dose of 100 μg/mL of rutin were 3.5% MN counted, whereas for a similar dose treatment with rutin-ester a frequency of 8% of MN was found. The fact that rutin-ester is causing significantly higher levels of MN than the rutin alone can be considered as a manifestation of a higher action of the agent on the chromosome owing to its easier penetration in to the cell after its esterification.     

Modelling of solid oxide proton conducting reactor-cells: thermodynamics and kinetics

A model is prepared for hydro- and dehydrogenation reactions that are carried out in solid electrolyte cell-reactors. Hydrogen is supplied in the form of H⁺ through the proton conducting wall and the thermodynamic activity of hydrogen on the catalyst surface is controlled electrochemically. Three reactor types are considered, a plug flow reactor, a well-mixed reactor and a “single-chamber” cell in which both electrodes are exposed to the same reacting mixture. Under certain conditions, the yield of the cell-reactor is orders of magnitude higher than that of the corresponding conventional catalytic reactor. The key parameters that affect the product yield as well as the conditions that must be met, are discussed. Experimental results for the reaction of methane dimerization studied with a strontia-ceria-ytterbia electrolyte on palladium electrodes, are presented and compared to model predictions. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Novel methodology for 3D reconstruction of carotid arteries and plaque characterization based upon magnetic resonance imaging carotid angiography data

In this study, we present a novel methodology that allows reliable segmentation of the magnetic resonance images (MRIs) for accurate fully automated three-dimensional (3D) reconstruction of the carotid arteries and semiautomated characterization of plaque type. Our approach uses active contours to detect the luminal borders in the time-of-flight images and the outer vessel wall borders in the T(1)-weighted images. The methodology incorporates the connecting components theory for the automated identification of the bifurcation region and a knowledge-based algorithm for the accurate characterization of the plaque components. The proposed segmentation method was validated in randomly selected MRI frames analyzed offline by two expert observers. The interobserver variability of the method for the lumen and outer vessel wall was -1.60%±6.70% and 0.56%±6.28%, respectively, while the Williams Index for all metrics was close to unity. The methodology implemented to identify the composition of the plaque was also validated in 591 images acquired from 24 patients. The obtained Cohen's k was 0.68 (0.60-0.76) for lipid plaques, while the time needed to process an MRI sequence for 3D reconstruction was only 30 s. The obtained results indicate that the proposed methodology allows reliable and automated detection of the luminal and vessel wall borders and fast and accurate characterization of plaque type in carotid MRI sequences. These features render the currently presented methodology a useful tool in the clinical and research arena.     

Development and validation of a liquid chromatography-electrosprayionization mass spectrometric method for the determination of dexamethasone in sheep plasma

A quantitative liquid chromatographic-electrospray ionization mass spectrometric method for the determination of dexamethasone in sheep plasma has been developed and validated. The samples were extracted using solid-phase extraction cartridges with mixed reversed-phase materials (oasis-HLB). The chromatographic separation was performed on a reversed-phase XTerrra MS C₁₈ column ( mm; 5 μm) using a mobile phase consisting of 65% methanol in water containing 0.1% (v/v) formic acid, pumped at a flow rate of 0.30 ml min⁻¹. The analyte was detected after positive electrospray ionization using selected ion monitoring (SIM) mode. The probe heater temperature was set at 260 °C, the capillary voltage was set at 3.5 kV and the source block voltage (AQA_max) was set at 30 V. The method was fully validated. Calibration graphs were linear (r better than 0.998, n=11), in concentration ranges 6-1000 ng ml⁻¹ for dexamethasone. The intra- and inter-day RSD values were less than 24.1% (n=6). The limits of detection and quantitation for dexamethasone were found to be 1 and 6 ng ml⁻¹, respectively. The efficiency of the solid phase extraction procedure was found to be 92.4% for dexamethasone. The method was further applied to a pilot kinetic study in order to assess the main pharmacokinetic parameters of dexamethasone in sheep.     

CFD modeling of a biogas fuelled SOFC

Mathematical modeling of transport and electrochemical phenomena within SOFCs can lead to improved understanding of the involved physical, electrical, and chemical processes and represents a powerful tool for their development. In this context, the present work illustrates a three-dimensional CFD simulation of a planar SOFC unit cell fuelled by modeled biogas/steam mixtures. The simulations estimate the distribution of gas species, the current densities and the potentials, as well as the temperature gradients and confirm that equimolar CH₄/CO₂ biogas leads to improved performance, while minimal steam addition can prevent carbon deposition.