Improving Separation Efficiency in End-of-Life Lithium-Ion Batteries Flotation Using Attrition Pre-Treatment

The comminution of spent lithium-ion batteries (LIBs) produces a powder containing the active cell components, commonly referred to as “black mass.” Recently, froth flotation has been proposed to treat the fine fraction of black mass (<100 µm) as a method to separate anodic graphite particles from cathodic lithium metal oxides (LMOs). So far, pyrolysis has been considered as an effective treatment to remove organic binders in the black mass in preparation for flotation separation. In this work, the flotation performance of a pyrolyzed black mass obtained from an industrial recycling plant was improved by adding a pre-treatment step consisting of mechanical attrition with and without kerosene addition. The LMO recovery in the underflow product increased from 70% to 85% and the graphite recovery remained similar, around 86% recovery in the overflow product. To understand the flotation behavior, the spent black mass from pyrolyzed LIBs was compared to a model black mass, comprising fully liberated LMOs and graphite particles. In addition, ultrafine hydrophilic particles were added to the flotation feed as an entrainment tracer, showing that the LMO recovery in overflow products is a combination of entrainment and true flotation mechanisms. This study highlights that adding kerosene during attrition enhances the emulsification of kerosene, simultaneously increasing its (partial) spread on the LMOs, graphite, and residual binder, with a subsequent reduction in selectivity.

Parachute structure trisiloxane surfactant: synthesis and its use in reverse flotation of iron ore

No single element has exerted such a deep influence on social organization of mankind as iron. Magnetite is concentrated by froth flotation and used as a raw material to produce iron. However, the conventional surfactants used in the flotation process often lead to the weak collecting performance due to their analogous alkyl hydrophobic group. Here, we report a new trisiloxane surfactant N-(β-aminoethyl)-γ-aminopropyltrisiloxane (AAT) in magnetite flotation, which was compared with the traditional collector dodecylamine (DA). The flotation test results showed that AAT had excellent collecting ability and selectivity for quartz against magnetite. Magnetite concentrate with TFe recovery of 84.79%, TFe grade of 68.84% and SiO2 grade of 6.15% was obtained by using 150 g/t AAT. Density functional theory calculations suggested reactive site of AAT was cationic –CH2N+H3 group, and AAT showed a higher positive grouping Mulliken charge and chemical reactivity that may promote its flotation performance.

Lead Recovery from a Lead Concentrate throughout Direct Smelting Reduction Process with Mixtures of Na2CO3 and SiC to 1000 °C

Lead was recovered through a direct smelting reduction route from a lead concentrate by using mixtures of Na2CO3 and SiC to 1000 °C. The lead concentrate was obtained from the mining State of Zacatecas, México by traditional mineral processing and froth flotation. The experimental trials showed that 86 wt.% of lead with a purity up to 97% can be recovered from the lead concentrate by a single step reduction process when 40 wt.% Na2CO3 and 0.4 g SiC were used in the initial charge. The process was modeled in the thermodynamic software FactSage 7.3 to evaluate the effect of adding different amounts of Na2CO3 on the lead recovery rates while holding constant the SiC amount and temperature. The stability phase diagram obtained showed that an addition of 34 wt.% Na2CO3 was enough to reach the highest lead recovery. It was observed that the interaction of Na2CO3 and SiC at a high temperature promotes the formation of C and Na2O, and SiO2, respectively, where the Na2O partially bonds with silica and sulfur forming Na2S and sodium silicates which may decrease the SO2 emissions and increase the weather degradation of the slag. The PbS was mainly reduced by the produced C and CO formed by the interaction between Na2CO3 and SiC at 1000 °C. The predicted results reasonably match with those obtained experimentally in the lead recovery rates and compounds formation.

Recovery of Catapleiite and Eudialyte from Non-Magnetic Fraction of Eudialyte ore Processing of Norra Kärr Deposit

Eudialyte ores from Norra Kärr (Sweden) and Kringlerne (Greenland) are considered a potential source of rare-earth elements (REE) for the development of a sustainable REE industry outside China. Magnetic separation is successfully applicated to recover eudialyte as a magnetic fraction. In the case of the Norra Kärr deposit, up to 20% of the REE and up to 40% of the Zr are lost during mineral processing in the non-magnetic fraction. Zr and REE are associated with non-magnetic minerals such as catapleiite, low- or non-magnetic eudialyte species, and both their intergrowths. Besides zirconosilicates such as catapleiite and eudialyte, the non-magnetic fraction has valuable and already-liberated minerals such as alkali feldspars and nepheline, which should not be considered as tailings. In this investigation, a possible way to recover REE bearing zirconosilicates from the non-magnetic fraction using flotation is presented. First, a low-grade eudialyte concentrate (1.8% Zr, 0.94% REE) from ground ore was obtained using magnetic separation. The non-magnetic fraction was then treated using froth flotation, and a Zr-REE bearing product (9% Zr, 1.5% REE) was obtained as froth product. For this purpose, phosphoric acid esters were used as selective collectors for zirconosilicates at a pH between 3.5 and 4.5. The reagent regime could be proposed not only to recover Zr- and REE-bearing minerals, but also simultaneously to remove Fe, Ti, and other colored impurities from the nepheline-feldspar product and to minimize the tailings volume.

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.