The Electrical Conductivity of Molten Oxide-Fluoride Cryolite Mixtures

A new way to reduce the energy consumption during the operation of powerful aluminum reduction cells is suggested via reducing the resistance of the electrolyte, i.e., increasing its electrical conductivity. The electrical conductivity of molten cryolite mixtures NaF-AlF3-CaF2-Al2O3 with cryolite ratio (CR) of 2.1–3.0 and content of CaF2 and Al2O3, up to 8 wt%, was measured at the temperatures from liquidus to 1300 K. Based on the experimental results, a multifunctional equation for the electrical conductivity of oxide-fluoride cryolite melts was evaluated. The experimental and calculated values of the electrical conductivity agree within 1.5%. The activation energy of the electrical conductivity of the NaF-AlF3-CaF2-Al2O3 melts was estimated. The activation energy of electrical conductivity for molten NaF-AlF3 mixtures with CR 3.0 and 2.1, determined by the most mobile cations Na+, increased from 15.8 kJ/mol up to 18.5 kJ/mol. It was found that CR had a greater impact on the activation energy than the changes in the Al2O3 or CaF2 concentrations. Based on the ratio of the activation energies of the electrical conductivity and the viscous flow, the correlation between the electrical conductivity and viscosity of molten cryolite mixtures NaF-AlF3-CaF2-Al2O3 was illustrated.

Effect of Al2O3 and CaF2 additives on the viscosity of conventional cryolite melts

The viscosity of cryolite melts of conventional composition NaF–AlF3–CaF2–Al2O3 was studied by rotational viscometry using the FRS 1600 high-temperature rheometer. The cryolite ratio of the NaF–AlF3 melt was 2.1, 2.3, and 2.5; the Al2O3 content varied from 2 to 6.6, and CaF2 – from 0 to 8 wt%. The measurements were carried out in the temperature range from liquidus to 1200 °C. The conditions for the laminar flow of the investigated melts were determined, based on the measurements of the cryolite melts viscosity as a function of the shear rate at a constant temperature. A shear rate of 12 ± 1 s–1 was chosen for studying the viscosity temperature dependence for all samples. The viscosity temperature dependence of cryolite melts is described by a linear equation. The temperature coefficient b in this equation has negative values and varies in the range of (–0.01)–(–0.06) mPa·s/deg. It was found that the viscosity of cryolite melts of conventional composition in the range of operating temperatures of aluminum electrolysis (950–970 °C) varies from 2.5 to 3.7 mPa·s (depending on the composition and temperature). The viscosity of cryolite-alumina melts increases with the rise of alumina content: 1 wt% Al2O3 increases the viscosity, on average, by 1%. However, the influence of CaF2 is more significant: the addition of 1 wt% CaF2 leads to an increase in viscosity by 3%. A decrease in the CR of the melt by 0.1 (in the range of 2.1–2.5) leads to a decrease in the viscosity of cryolite melts by 2.3%. A viscosity regression equation for the cryolite melts of conventional composition as a function of several independent parameters (temperature, CR, CaF2 and Al2O3 content) is obtained by the multivariable approximation of experimental data. The equation satisfactorily (within 1.5%) describes the viscosity of conventional industrial electrolytes and can be used for estimation of their viscosity.

Densities and electrochemical potential window of the BaCl2-NaCl-NaF-AlF3 electrolyte

The effect of melt composition (BaCl2-NaCl-NaF-AlF3) on its density, resistivity and redox potentials of the main electrode processes is reported. A three-factor two-level experimental design was used to study the effects of cryolite ratio (1.1-1.6) and BaCl2 (0-60wt%) or NaCl (0-10wt%) content on the melt density. The obtained equation satisfactorily describes the measured melt densities. The observed non-linear behavior of melt density with BaCl2 additions is assigned to the formation of BaClF complex. Unlike BaCl2, additions of 0-10 wt% NaCl have little effect on the melt density, however, affect the melt conductivity significantly.

Production of the Al–B master alloy by KBF4and B 2O3aluminothermic reduction in molten salt flux medium

The study covers the process of obtaining the Al–B master alloy by the KBF4and B2O3aluminothermic reduction using KF–AlF3and KF–NaF–AlF3fluoride fluxes at 983 and 1123 К, respectively, and KCl–NaCl–KF chloride-fluoride fluxes at Т= 1173÷1223 К. All experiments were carried out under the same conditions: molten mixture stirring rate was 400 rpm, synthesis duration was 30min. The maximum amount of boron (1,5 %) in the Al–B alloy was obtained when using KBF4(3 % per B) as a boron-containing raw material in the KF–AlF3medium with a molar (cryolite) ratio (CR) of KF/AlF3equal to 1,3, atТ= 983 К, while boron recovery ratio did not exceed 75 %. Comparable results were obtained in experiments with KF–NaF–AlF3f lux (CR = 1,5) at Т= 1123 К. However, with the increased concentration of fed boron its recovery ratio decreased substantially. It is connected with the higher decomposition temperature of not only KBF4, but also less thermally stable NaBF4 formed as a result of exchange reaction in the melt. Therefore it is not recommended to use sodium salts as a f lux component. The Al–B master alloys obtained by KBF4reduction in fluoride fluxes were solid solutions of B in Al containing the AlB2intermetallic compound. The lowest amount of boron in aluminum with the minimum degree of extraction was obtained in experiments with the B2O3in molten KF–AlF3with CR = 1,5. Nevertheless, the results of scanning electron microscopy indicate a uniform distribution of B over the Al matrix and the absence of intermetallic compounds, while a large amount of Al2O3was found, which is the product of B2O3reactions with both liquid Al and KF–AlF3flux.

INFLUENCE OF ELECTROLYTE COMPOSITION AND OVERHEATING ON THE SIDELEDGE IN THE ALUMINUM CELL

The paper presents a theoretical study conducted to investigate the effect that the chemical composition of electrolyte and its overheating have on the size of sideledge formed in an aluminum smelting bath. Three electrolyte compositions were chosen: (1) sodium cryolite with the cryolite ratio CR = 2,7; (2) cryolite CR = 2,7 + 5 wt.% CaF2; (3) cryolite CR = 2,7 + 5 wt.% CaF2 + 5 wt.% Al2О3. The electrolyte liquidus overheating temperatures were 5, 10, 15 and 20 °C. Calculations were performed using the finite element method. A simplified design of an aluminum cell was used with a prebaked anode. The temperature field was calculated using a mathematical model based on the Boussinesq approximation, which contains the Navier–Stokes equation as well as thermal conductivity and incompressibility equations. The key role of electrolyte overheating in sideledge formation was established. The resulting sideledge profile depends on the heat transfer coefficients and thermophysical properties of materials. The smallest sideledge thickness with the same electrolyte overheating was observed in cryolite composition 3, and the profiles of the formed sideledge for samples 1 and 2 were nearly the same. The thickness of the sideledge formed with a 5 degree overheating exceeded 7 cm and the difference in temperature between the sideledge in contact with electrolyte and the side block wall was 20–25 degrees. It was found that the virtually total disappearance of the sideledge occurs at electrolyte liquidus overheating by 20 degrees.