Rare Earths and the Balance Problem: How to Deal with Changing Markets?

The balance between the market demand and the natural abundance of the rare-earth elements (REEs) in ores, often referred to as the Balance Problem (or the Balancing Problem), is a major issue for REE suppliers. The ideal situation is a perfect match between the market demand for and the production of REEs, so that there are no surpluses of any of the REEs. This means that the rare-earth industry must find new uses for REEs that are available in excess and search for substitutes for REEs that have either limited availability or are high in demand. We present an overview of the trends in the applications for the different REEs and show that the demand for REEs for use in magnets, catalysts, and alloys is still increasing, while the application of REEs in polishing agents, glass, and ceramics are stable. On the other hand, the use of REEs in nickel–metal-hydride (NiMH) batteries and lamp phosphors is decreasing. These changes in the REE market have an influence on the Balance Problem, because the REEs that can be recycled from fluorescent lamps, cathode-ray tubes (CRTs), and NiMH batteries have to be at least partly reused in other applications. Magnesium and aluminum alloys offer an opportunity to mitigate the Balance Problem caused by these changes in the REE market. This is illustrated for REEs that can be recycled from fluorescent-lamp phosphor waste, CRT phosphors, and NiMH batteries. At present, five REEs (Nd, Eu, Tb, Dy, and Y) are being considered as very critical by Europe, the United States, and Japan, but we forecast that in the medium term, only neodymium will remain a critical REE. This paper discusses the relationship between criticality and the Balance Problem and shows how this relationship influences the market for specific REEs.This work has received funding from the European Union’s Horizon 2020 research and innovation programme under Grant Agreement No 680629 (REMAGHIC: New Recovery Processes to produce Rare Earth-Magnesium Alloys of High Performance and Low Cost) (project website: http://www.remaghic-project. eu). KB and PTJ acknowledge funding from the European Community’s Seventh Framework Programme ([FP7/2007–2013]) under Grant Agreement No. 607411 (MC-ITN EREAN: European Rare Earth Magnet Recycling Network) (project website of EREAN: http:// www.erean.eu). Paul McGuiness (Sciencewriter.si, Slovenia) is acknowledged for the drawing of the figures

Los residuos industriales como reactivos para el secuestro de CO2

La carbonatación mineral es una interesante vía para elsecuestro de dióxido de carbono de una forma permanentey segura. Esta tecnología aplicada a los residuosindustriales es una alternativa que podría contribuir a ladisminución de las emisiones de CO 2 a la atmósfera. Elobjetivo de este trabajo consiste en estudiar la viabilidaddel almacenamiento del dióxido de carbono mediante eltratamiento del gas con diferentes fuentes de residuos. Elmétodo desarrollado es el denominado “carbonatación directagas-sólido” que consiste en la captación de dióxidode carbono mediante su reacción con el residuo en condicionesde tiempo y temperatura controladas. A tal fin, seha llevado a cabo el diseño y puesta a punto de un sistemaexperimental a nivel de laboratorio para la captura de CO 2gas mediante residuos. La evaluación del proceso se harealizado mediante la aplicación de diferentes metodologíasde análisis cuantitativo y estructural. El estudio se haaplicado a diversas tipologías de residuos tales como lascenizas de incineración de residuos sólidos urbanos, lasescorias blancas de acería de horno de arco eléctrico, lasescorias negras de acería de horno de arco eléctrico y lasescorias de procesos Waelz

Enhancing rare-earth recovery from lamp phosphor waste

In the present work rare-earth recovery was performed from a residue of a hydrometallurgical process based on sulphuric acid leaching of lamp phosphor waste by which the red phosphor Y2O3:Eu3+ was removed for further recovery. The undissolved residue is rich in lanthanum, cerium and the valuable terbium, present as phosphates and aluminates in the green and blue phosphors. The process here proposed is based on an integrated pyro-hydrometallurgical approach involving a thermal treatment (roasting in the presence of sodium carbonate) aimed at converting rare-earth phosphates into oxides, which can be more easily leached by mineral acids (HCl and H2SO4) in a further leaching step. Rare-earth recovery from the leachate was then performed by solvent extraction with the extractant di-(2-ethylhexyl)phosphoric acid, D2EHPA, followed by precipitation with oxalic acid and calcination. 82% Ce, 75% La and 82% Tb were recovered as mixed La2O3 + CeO2 oxide (99% purity) and Tb4O7 (64% purity).This work has received funding from the European Union's Horizon2020 research and innovation programme under Grant Agreement No.680629 (REMAGHIC: New Recovery Processes to produce Rare Earth-Magnesium Alloys of High Performance and Low Cost) (project website:http://www.remaghic-project.eu/). The authors acknowledge Relightsrl for providing the lamp phosphor powder

Selective leaching of copper and zinc from primary ores and secondary mineral residues using biogenic ammonia

With the number of easily accessible ores depleting, alternate primary and secondary sources are required to meet the increasing demand of economically important metals. Whilst highly abundant, these materials are of lower grade with respect to traditional ores, thus highly selective and sustainable metal extraction technologies are needed to reduce processing costs. Here, we investigated the metal leaching potential of biogenic ammonia produced by a ureolytic strain of Lysinibacillus sphaericus on eight primary and secondary materials, comprised of mining and metallurgical residues, sludges and automotive shredder residues (ASR). For the majority of materials, moderate to high yields (30–70%) and very high selectivity (>97% against iron) of copper and zinc were obtained with 1 mol L−1 total ammonia. Optimal leaching was achieved and further refined for the ASR in a two-step indirect leaching system with biogenic ammonia. Copper leaching was the result of local corrosion and differences in leaching against the synthetic (NH4)2CO3 control could be accounted for by pH shifts from microbial metabolism, subsequently altering free NH3 required for coordination. These results provide important findings for future sustainable metal recovery technologies from secondary materials.This work was conducted under the financial support of the Strategic Initiative Materials in Flanders (SIM) (SBO-SMART: Sustainable Metal Extraction from Tailings, grant no. HBC.2016.0456) and the European Union’s Horizon 2020 research and innovation programme, Metal Re-covery from Low-Grade Ores and Wastes Plus (METGROW+, grant no. 690088) . FV acknowledges support by the Flemish Agency for Inno-vation and Entrepreneurship (Vlaio) via a Baekeland PhD fellowship (HBC.2017.0224) and by the Research & Development Umicore Group. We would like to thank Pieter Ostermeyer and Karel Folens for assis-tance with thermodynamic modelling and CMET and ECOCHEM group members and SMART/METGROW+partners for valuable discussions throughout the projec

Bioleaching of metals from secondary materials using glycolipid biosurfactants

With the global demand for economically important metals increasing, compounded by the depletion of readily accessible ores, secondary resources and low-grade ores are being targeted to meet growing demands. Novel technologies developed within biobased industries, such as microbial biosurfactants, could be implemented to improve the sustainability of traditional hydrometallurgy techniques. This study investigates newly developed microbial biosurfactants (acidic- and bolaform glycolipids) for the leaching of metals (particularly Cu and Zn) from a suite of mine tailings, metallurgical sludges and automotive shredder residues. Generally, acidic sophorolipids were the most performant, and optimal Cu leaching was observed from a fayalite slag (27%) and a copper sulfide mine tailing (53%). Further investigation of the leached fayalite material showed that leaching was occurring from small metallic Cu droplets in this material via a corrosion-based mechanism, and/or from Cu-Pb sulfides, selective against dominant Fe-silicate matrices. This study highlights that acidic sophorolipid microbial biosurfactants have the potential to leach Cu and Zn from low-grade secondary materials. It also provides important fundamental insights into biosurfactant-metal and mineral interactions that are currently unexplored. Together, the convergence of leaching and mining industries with bio-industries can improve material recovery and will positively impact the bio- and circular economies and the environment.The authors thank Bio Base Europe Pilot plant for supplying the biosurfactants that enabled the execution of the leaching experiments. We also thank Joachim Neri, Karel Folens, Nina Ricci Nicomel and Melgü Kizilmese for their assistance during ICP-analyses

Near-zero-waste processing of low-grade, complex primary ores and secondary raw materials in Europe: technology development trends

With an increasing number of low-grade primary ores starting to be cog-effectively mined, we are at the verge of mining a myriad of low-grade primary and secondary mineral materials. At the same time, mining practices and mineral waste recycling are both evolving towards sustainable near-zero-waste processing of low-grade resources within a circular economy that requires a shift in business models, policies and improvements in process technologies. This review discusses the evolution towards low-grade primary ore and secondary raw material mining that will allow for sufficient supply of critical raw materials as well as base metals. Seven low-grade ores, including primary (Greek and Polish laterites) and secondary (fayalitic slags, jarosite and goethite sludges, zincrich waste treatment sludge and chromium-rich neutralisation sludge) raw materials are discussed as typical examples for Europe. In order to treat diverse and complex low-grade ores efficiently, the use of a new metallurgical systems toolbox is proposed, which is populated with existing and innovative unit operations: (i) mineral processing, (ii) metal extraction, (iii) metal recovery and (iv) matrix valorisation. Several promising novel techniques are under development for these four unit-operations. From an economical and environmental point of view, such processes must be fitted into new (circular) business models, whereby impacts and costs are divided over the entire value chain. Currently, low-grade secondary raw material processing is only economic and environmentally beneficial when the mineral residues can be valorised and landfill costs are avoided and/or incentives for waste processing can be taken into account

A Sustainable Process for the Recovery of Valuable Metals from Spent Lithium Ion Batteries by Deep Eutectic Solvents Leaching

The feasibility of using low-environmental-impact leaching media to recover valuable metals from lithium ion batteries (LIBs) has been evaluated. Several deep eutectic solvents (DES) were tested as leaching agents in the presence of different type of additives (i.e., H2O2). The optimization of Co recovery was carried out by investigating various operating conditions, such as reaction time, temperature, solid (black mass) to liquid (DES) ratio, additive type, and concentration. Leaching with final selected DES choline chloride (33%), lactic acid (53%), and citric acid (13%) at 55 °C achieved an extraction yield of more than 95% for the cobalt. The leaching mechanism likely begins with the dissolution of the active material in the black mass (BM) followed by chelation of Co(II) with the DES. The results obtained confirm that those leaching media are an eco-friendly alternative to the strong inorganic acids used nowadays

Recovery of Tungsten from Downstream Mineral Processing Fractions by Deep Eutectic Solvents

Tungsten is a scarce and valuable metal with a wide range of applications. Currently, the recovery of tungsten from scheelite concentrates involves the use of strong acids, alkalis, and/or high temperatures (roasting). Deep Eutectic Solvents (DES) are proposed as an environmentally friendly alternative for the leaching process aiming to extract the tungsten contained. In this work, high grade scheelite concentrate (W 57%) was the material used for the investigation. After an exhaustive DES screening, choline chloride-oxalic acid (ChCl/OA)-based DES showed the best leaching performance. An optimization of the leaching variables (temperature, time, liquid/solid ratio, ChCl/OA ratio) was carried out. A W extraction yield as high as 95% was achieved at certain operating conditions

Industrial waste residues evaluation: D 1.1

This report contains an evaluation of the main REE-containing industrial waste residues considered in WP1. The objectives are: (1) to characterize the input waste materials by analyzing the main chemical composition, with focus on the REE, and (2) to identify the most promising waste streams for further study in the REMAGHIC project. Relight provided the research partners with industrial waste recovered from electronic components. ITRB evaluated other industrial waste like phosphogypsum and metallurgical slags. An industrial waste material has been selected and Tecnalia carried out the analyses and gathered information on the homogeneity/heterogeneity of the waste material. The outcome is a waste classification according to the concentration of the most interesting REE for the project (Y, Ce, La), taking into account the information about the presence of other REE. The most interesting REE-containing waste streams are: fluorescent lamp phosphors, CRT phosphors and NiMH batteries. The selected materials were collected and sent to the research partners for evaluation of different recovery techniques within the other WP1 tasks. Ref. Ares(2016)2775100 - 15/06/2016H2020 – SPIRE – 2015 – Grant Agreement 680629 – Project REMAGHICREMAGHIC Deliverable 1 1 V