Recovering Value from End-of-Life Batteries by Integrating Froth Flotation and Pyrometallurgical Copper-Slag Cleaning

In this study, industrial lithium-ion battery (LIB) waste was treated by a froth flotation process, which allowed selective separation of electrode particles from metallic-rich fractions containing Cu and Al. In the flotation experiments, recovery rates of ~80 and 98.8% for the cathode active elements (Co, Ni, Mn) and graphite were achieved, respectively. The recovered metals from the flotation fraction were subsequently used in high-temperature Cu-slag reduction. In this manner, the possibility of using metallothermic reduction for Cu-slag reduction using Al-wires from LIB waste as the main reductant was studied. The behavior of valuable (Cu, Ni, Co, Li) and hazardous metals (Zn, As, Sb, Pb), as a function of time as well as the influence of Cu-slag-to-spent battery (SB) ratio, were investigated. The results showcase a suitable process to recover copper from spent batteries and industrial Cu-slag. Cu-concentration decreased to approximately 0.3 wt.% after 60 min reduction time in all samples where Cu/Al-rich LIB waste fraction was added. It was also showed that aluminothermic reduction is effective for removing hazardous metals from the slag. The proposed process is also capable of recovering Cu, Co, and Ni from both Cu-slag and LIB waste, resulting in a secondary Cu slag that can be used in various applications.

Sulfonitrocarburizing of High-Speed Steel Cutting Tools: Kinetics and Performances

The scholarly literature records information related to the performance increase of the cutting tools covered by the superficial layers formed “in situ” when applying thermochemical processing. In this context, information is frequently reported on the carbamide role in processes aiming carbon and nitrogen surface saturation. Sulfur, together with these elements adsorbed and diffused in the cutting tools superficial layers, undoubtedly ensures an increase of their operating sustainability. The present paper discusses the process of sulfonitrocarburizing in pulverulent solid media of high-speed tools steel (AISI T1, HS18-0-1) and its consequences. The peculiarity of the considered process is that the source of nitrogen and carbon is mainly carbamide (CON2H4), which is found in solid powdery mixtures together with components that do not lead to cyan complex formation (non-toxic media), and the sulfur source is native sulfur. The kinetics of the sulfonitrocarburizing process, depending on the carbamide proportion in the powdered solid mixture and the processing temperature, was studied. The consequences of the achieved sulfonitrocarburized layers on the cutting tools’ performance are expressed by the maximum permissible cutting speed and the maximum cut length. An interesting aspect is highlighted, namely the possibility of using chemically active mixtures. Their components, by initiation of the metallothermic reduction reaction, become able to provide both elements of interest and the amount of heat needed for the ultrafast saturation of the targeted metal surfaces.

A new method for determining stoichiometric coefficients using minors of a matrix

The motivation of this study was the investigation into the metallothermic reduction of chromite ores. Spinel materials have complex structures and as a result, balancing of the reduction reactions by traditional methods become very time consuming. A method to calculate the stoichiometric coefficients for chemical reactions using first a modified matrix-inverse method and then a new optimised method is proposed. The mathematical basis of both methods is explored using matrix algebra and then demonstrated using a typical chromite reduction reaction.

Thermodynamic Studies and Optimization of the Method for Obtaining Neodymium Fluoride for the Production of Magnetic Sensors’ Sensitive Elements

Rare earth metals (REM) with magnetic properties find application in the recently developed high-tech industries. Sensor magnetic systems based on neodymium are increasingly in demand in modern engineering and geological surveys due to their favorable combination of properties of magnetic materials based on rare earth metals. One of the problems is to obtain high-quality materials for the production of such magnetic sensors. It should be noted that the high activity of REM does not allow obtaining master alloys and REM-based alloys from metallic materials; it is advisable to use halide compounds. This work discusses a method for producing neodymium fluoride from its oxide. REM fluorides can be obtained by fluorinating the oxides of these metals. Various fluorine-containing compounds or elemental fluorine are usually used as fluorinating reagents, which have their own advantages and disadvantages. The thermodynamic and technological analysis of neodymium fluoride production processes has shown the most acceptable fluorinating agent is ammonium hydrofluoride, which was used in this work. In order to increase the productivity and degree of chemical transformation, it was proposed to perform heating stepwise; i.e., at the initial stage, heat at a speed of 3 degrees per minute, after which the heating speed was reduced to 2 degrees per minute, and finally the speed was reduced to 1 degree per minute. Due to proposed heating mode, the same productivity and yield of chemical transformation were achieved, with an increased efficiency up to 30%, which can significantly reduce the cost of production. The obtained product is used in the production of neodymium-based alloys by metallothermic reduction of a mixture of fluorides. The sensor material obtained in this way is characterized by a low (less than 0.05%) oxygen content.

Microstructural Master Alloys Features of Aluminum–Erbium System

Aluminum master alloys with rare earth metals are widely studied by many scientists around the world, but research on the production of Al-Er master alloys is still limited. The purpose of this work is to study the microstructure parameters of aluminum-erbium master alloys obtained by metallothermic reduction of salt mixtures containing erbium oxide or fluoride. The structural features were investigated by optical and scanning electron microscopy, and the dependence of the microhardness of the eutectic and solid solution fields of obtained master alloys on the content of erbium in the master alloy was determined. Studies have shown that master alloys obtained by metallothermic reduction of erbium compounds from chloride–fluoride melts are characterized by a uniform distribution of Al3Er intermetallic compounds in the volume of double eutectic [(Al) + Al3Er] and have a strong grain refinement effect. The analysis of the microstructure showed that the structure of the master alloys varies depending on the content of erbium. When the content of erbium in the master alloy is up to 6 wt.%, the eutectic structure is preserved. When the content of erbium in the master alloy is 8 wt.% or more, the structure becomes a solid solution with individual inclusions of various shapes and intermetallic compounds.

Study on the fluorination of dysprosium oxide by ammonium bifluoride for the preparation of dysprosium fluoride

In this report, dysprosium fluoride (DyF3) - a material for the preparation of dysprosium (Dy) metal was prepared by the fluorination of dysprosium oxide (Dy2O3) by ammonium bifluoride (NH4HF2) reagent. The effect of reaction time and temperature on the formation of dysprosium fluoride salt has been studied. The phase composition and crystal structure of the obtained products were analysed by X-ray diffraction (XRD). Thermal analysis techniques were applied to determine the temperature range of the fluorination. Scanning electron microscopy with energy dispersive spectroscopy (SEM/EDS) was used for external morphology observation and chemical elemental composition analysis. The results showed that the high purity phase of DyF3 was formed at the conditions: reaction time and temperature of >1 h and >350oC, respectively. The product is available for the preparation of Dy metal by metallothermic reduction.

Metallothermic Reduction of MoO3 on Combustion Synthesis of Molybdenum Silicides/MgAl2O4 Composites

Combustion synthesis involving metallothermic reduction of MoO3 by dual reductants, Mg and Al, to enhance the reaction exothermicity was applied for the in situ production of Mo3Si–, Mo5Si3− and MoSi2–MgAl2O4 composites with a broad compositional range. Reduction of MoO3 by Mg and Al is highly exothermic and produces MgO and Al2O3 as precursors of MgAl2O4. Molybdenum silicides are synthesized from the reactions of Si with both reduced and elemental Mo. Experimental evidence indicated that the reaction proceeded as self-propagating high-temperature synthesis (SHS) and the increase in silicide content weakened the exothermicity of the overall reaction, and therefore, lowered combustion front temperature and velocity. The XRD analysis indicated that Mo3Si–, Mo5Si3– and MoSi2–MgAl2O4 composites were well produced with only trivial amounts of secondary silicides. Based on SEM and EDS examinations, the morphology of synthesized composites exhibited dense and connecting MgAl2O4 crystals and micro-sized silicide particles, which were distributed over or embedded in the large MgAl2O4 crystals.

Pyrometallurgy and Electrometallurgy of Rare Earths – Part A: Analysis of Metallothermic Reduction and its Variants

Rare earths are classified as most important and critical material for US economy and defense by Congress and a mandate has been set to increase their in-house production, domestic resource utilization and decrease reliance on foreign resources and reserves. They are widely available in earth crust as ore (bastnaesite (La, Ce)FCO3, monazite, (Ce, La, Y, Th)PO4, and xenotime, YPO4), but their so-called economic reserves are sparsely located geographically. They may be produced by various means such as beneficiation (physical, chemical, mechanical, or electrical), reduction (direct or indirect), electrolysis (of aqueous or molten / fused single or mixed salt systems) at high temperature or hydrometallurgy. Out of these, direct reduction also known as metallothermic reduction (La and Ca reduction) is mostly utilized. Its variant, high temperature electrowinning of fused salts is also practiced widely. These processes are material and application specific. In this study, author will employ thermodynamics (Ellingham diagrams, free energy of formation, reduction potential, Nernst equation, Pourbaix (Eh-pH) diagrams, E-pO-2 diagrams), kinetics and energetic of a chemical reaction (chemical metallurgy) to reduce rare earth oxide / salt to rare earth metals (REO/RES – REM). It is shown that materials and energy requirement vary greatly depending on type of mineral ore, production facility, and beneficiation / mineral processing method selected. Aim is to reduce dependence on coal deposits. It is anticipated this route will be able to produce rare earths with > 35% yield and > 98% purity which be described in subsequent studies and patents.