With the increasing demand for electronic products, the amount of multilayer ceramic capacitor (MLCC) waste has also increased. Recycling technology has recently gained attention because it can simultaneously address raw material supply and waste disposal issues. However, research on recovering valuable metals from MLCCs and converting the recovered metals into high-value-added materials remains insufficient. Herein, we describe an electrospinning (E-spinning) process to recover nickel from MLCCs and modulate the morphology of the recovered nickel oxide particles. The nickel oxalate powder was recovered using organic acid leaching and precipitation. Nickel oxide nanoparticles were prepared via heat treatment and ultrasonic milling. A mixture of nickel oxide particles and polyvinylpyrrolidone (PVP) was used as the E-spinning solution. A PVP/NiO nanowire composite was fabricated via Espinning, and a nickel oxide nanowire with a network structure was manufactured through calcination. The nanowire diameters and morphologies are discussed based on the nickel oxide content in the E-spinning solution.
Cobalt is a vital metal in the modern society because of its applications in lithium-ion batteries, super alloys, hard metals, and catalysts. Further, cobalt is a representative rare metal and is the 30th most abundant element in the Earth’s crust. This study reviews the current status of cobalt extraction and recycling processes, along with the trends in its production amount and use. Although cobalt occurs in a wide range of minerals, such as oxides and sulfides of copper and nickel ores, the amounts of cobalt in the minerals are too low to be extracted economically. The Democratic Republic of Congo (DRC) leads cobalt mining, and accounts for 68.9 % of the global cobalt reserves (142,000 tons in 2020). Cobalt is mainly extracted from copper–cobalt and nickel–cobalt concentrates and is occasionally extracted directly from the ore itself by hydro-, pyro-, and electro-metallurgical processes. These smelting methods are essential for developing new recycling processes to extract cobalt from secondary resources. Cobalt is mainly recycled from lithium-ion batteries, spent catalysts, and cobalt alloys. The recycling methods for cobalt also depend on the type of secondary cobalt resource. Major recycling methods from secondary resources are applied in pyro- and hydrometallurgical processes.
Citations
Tungsten carbide is widely used in carbide tools. However, its production process generates a significant number of end-of-life products and by-products. Therefore, it is necessary to develop efficient recycling methods and investigate the remanufacturing of tungsten carbide using recycled materials. Herein, we have recovered 99.9% of the tungsten in cemented carbide hard scrap as tungsten oxide via an alkali leaching process. Subsequently, using the recovered tungsten oxide as a starting material, tungsten carbide has been produced by employing a self-propagating high-temperature synthesis (SHS) method. SHS is advantageous as it reduces the reaction time and is energy-efficient. Tungsten carbide with a carbon content of 6.18 wt % and a particle size of 116 nm has been successfully synthesized by optimizing the SHS process parameters, pulverization, and mixing. In this study, a series of processes for the highefficiency recycling and quality improvement of tungsten-based materials have been developed.
Cobalt (Co) is mainly used to prepare cathode materials for lithium-ion batteries (LIBs) and binder metals for WC-Co hard metals. Developing an effective method for recovering Co from WC-Co waste sludge is of immense significance. In this study, Co is extracted from waste cemented carbide soft scrap via mechanochemical milling. The leaching ratio of Co reaches approximately 93%, and the leached solution, from which impurities except nickel are removed by pH titration, exhibits a purity of approximately 97%. The titrated aqueous Co salts are precipitated using oxalic acid and hydroxide precipitation, and the effects of the precipitating agent (oxalic acid and hydroxide) on the cobalt microstructure are investigated. It is confirmed that the type of Co compound and the crystal growth direction change according to the precipitation method, both of which affect the microstructure of the cobalt powders. This novel mechanochemical process is of significant importance for the recovery of Co from waste WC-Co hard metal. The recycled Co can be applied as a cemented carbide binder or a cathode material for lithium secondary batteries.
Here, we report the development of a new and low-cost core-shell structure for lithium-ion battery anodes using silicon waste sludge and the Ti-ion complex. X-ray diffraction (XRD) confirmed the raw waste silicon sludge powder to be pure silicon without other metal impurities and the particle size distribution is measured to be from 200 nm to 3 μm by dynamic light scattering (DLS). As a result of pulverization by a planetary mill, the size of the single crystal according to the Scherrer formula is calculated to be 12.1 nm, but the average particle size of the agglomerate is measured to be 123.6 nm. A Si/TiO2 core-shell structure is formed using simple Ti complex ions, and the ratio of TiO2 peaks increased with an increase in the amount of Ti ions. Transmission electron microscopy (TEM) observations revealed that TiO2 coating on Si nanoparticles results in a Si-TiO2 core-shell structure. This result is expected to improve the stability and cycle of lithium-ion batteries as anodes.
Because of its unique properties, tungsten is a strategic and rare metal used in various industrial applications. However, the world's annual production of tungsten is only 84000 t. Ammonium paratungstate (APT), which is used as the main intermediate in industrial tungsten production, is usually obtained from tungsten concentrates of wolframite and scheelite by hydrometallurgical treatment. Intermediates such as tungsten trioxide, tungsten blue oxide, tungstic acid, and ammonium metatungstate can be derived from APT by thermal decomposition or chemical attack. Tungsten metal powder is produced through the hydrogen reduction of high-purity tungsten oxides, and tungsten carbide powder is produced by the reaction of tungsten powder and carbon black powder at 1300–1700°C in a hydrogen atmosphere. Tungsten scrap can be divided into hard and soft scrap based on shape (bulk or powder). It can also be divided into new scrap generated during the production of tungsten-bearing goods and old scrap collected at the end of life. Recycling technologies for tungsten can be divided into four main groups: direct, chemical, and semi-direct recycling, and melting metallurgy. In this review, the current status of tungsten smelting and recycling technologies is discussed.
Citations
Rare earth magnets with excellent magnetic properties are indispensable in the electric device, wind turbine, and e-mobility industries. The demand for the development of eco-friendly recycling techniques has increased to realize sustainable green technology, and the supply of rare earth resources, which are critical for the production of permanent magnets, are limited. Liquid metal extraction (LME), which is a type of pyrometallurgical recycling, is known to selectively extract the metal forms of rare earth elements. Although several studies have been carried out on the formation of intermetallic compounds and oxides, the effect of oxide formation on the extraction efficiency in the LME process remains unknown. In this study, microstructural and phase analyses are conducted to confirm the oxidation behavior of magnets pulverized by a jaw crusher. The LME process is performed with pulverized scrap, and extraction percentages are calculated to confirm the effect of the oxide phases on the extraction of Dy during the reaction. During the LME p rocess, Nd i s completely e xtracted a fter 6 h, w hile D y remains as D y2Fe17 and Dy-oxide. Because the decomposition rate of Dy2Fe17 is faster than the reduction rate of Dy-oxide, the importance of controlling Dy-oxide on Dy extraction is confirmed.
Citations
Due to the rapid development of electricity, electronics, information communication, and biotechnology in recent years, studies are actively being conducted on nanopowders as it is required not only for high strengthening but also for high-function powder with electric, magnetic, and optical properties. Nonetheless, studies on nickel nanopowders are rare. In this study of the synthesis of nickel nanoparticles from LiNiO2 (LNO), which is a cathode active material, we have synthesized the nanosized nickel powder by the liquid reduction process of NiSO4 obtained through the leaching and purification of LNO. Moreover, we have studied the reduction reaction rate according to the temperature change of liquid phase reduction and the change of particle size as a function of NaOH addition amount using hydrazine monohydrate (N2H4·H2O) and NaOH.
This study focuses on the fabrication of a WC/Co composite powder from the oxide of WC/Co hardmetal scrap using solid carbon in a hydrogen gas atmosphere for the recycling of WC/Co hardmetal. Mixed powders are manufactured by mechanically milling the oxide powder of WC-13 wt% Co hardmetal scrap and carbon black with varying powder/ball weight ratios. The oxide powder of WC-13 wt% Co hardmetal scrap consists of WO3 and CoWO4. The mixed powder mechanically milled at a lower powder/ball weight ratio (high mechanical milling energy) has a more rapid carbothermal reduction reaction in the formation of WC and Co phases compared with that mechanically milled at a higher powder/ball weight ratio (lower mechanical milling energy). The WC/Co composite powder is fabricated at 900°C for 6 h from the oxide of WC/Co hardmetal scrap using solid carbon in a hydrogen gas atmosphere. The fabricated WC/Co composite powder has a particle size of approximately 0.25-0.5 μm.
Rare earth elements (REEs) are considered to be vital to modern industry due to their important roles in applications such as permanent magnets, automobile production, displays, and many more. The imbalance between demand and supply of REEs can be solved by recycling processes. Regarding the needs of industry and society, the International Organization for Standardization, Technical Committee 298 (ISO/TC298) Rare Earths has been recently launched for developing international standards on rare earth elements. In accordance with the suggestion of its constituents, it is tentatively working to develop the appropriate standards under five working groups (WG) on terms and definitions (WG1), element recycling (WG2), environmental stewardship (WG3), packaging, labelling, marking, transport, and storage (WG4), and testing analysis (WG5). The scope and structure of ISO/TC298 on the topic of rare earths is discussed in this document.
Citations
This study focuses on the development of an alkaline leaching hydrometallurgy process for the recovery of tungsten from WC/Co hardmetal sludge, and an examination of the effect of the process parameters on tungsten recovery. The alkaline leaching hydrometallurgy process has four stages, i.e., oxidation of the sludge, leaching of tungsten by NaOH, refinement of the leaching solution, and precipitation of tungsten. The WC/Co hardmetal sludge oxide consists of WO3 and CoWO4. The leaching of tungsten is most affected by the leaching temperature, followed by the NaOH concentration and the leaching time. About 99% of tungsten in the WC/Co hardmetal sludge is leached at temperatures above 90°C and a NaOH concentration above 15%. For refinement of the leaching solution, pH control of the solution using HCl is more effective than the addition of Na2S·9H2O. The tungsten is precipitated as high-purity H2WO4·H2O by pH control using HCl. With decreasing pH of the solution, the tungsten recovery rate increases and then decrease. About 93% of tungsten in the WC/Co hardmetal sludge is recovered by the alkaline leaching hydrometallurgy process.
Citations
Owing to increasing demand of rare metals present in ICT products, it is necessary to promote the rare metal recycling industry from an environmental viewpoint and to prevent climate change. Despite the fact that information for toxic substances is partly indicated, a legal basis and an international standard indicating usage of rare metals is insufficient. In order to address this issue, a newly created study group of environment and climate change at the ITU (International Telecommunication Union) is doing research to develop methodologies for recycling rare metals from ICT products in an eco-friendly way. Under this group, the Republic of Korea has established two international standards related to rare metals present in ICT products. The first is ‘Release of rare metal information for ICT products (ITU-T L.1100)’ and the other is ‘Quantitative and qualitative analysis methods for rare metals (ITU-T L.1101)’. A new proposal for recommending the provision of rare metal information through a label by manufacturers and consumer/recycling businesses has been approved recently and is supposed to be published later in 2016. Moreover, these recommendations are also being extended to IEC, ISO and other standardization organizations and a strategy to reinforce the ability for domestic standardization is being established in accordance with industrial requirements. This will promote efficient recycling of rare metals from ICT products and will help improve the domestic supply of rare metals.
Citations
The GaN-powder scrap generated in the manufacturing process of LED contains significant amounts of gallium. This waste can be an important resource for gallium through recycling of scraps. In the present study, the influence of annealing temperatures on the structural properties of GaN powder was investigated when the waste was recycled through the mechanochemical oxidation process. The annealing temperature varied from 200°C to 1100°C and the changes in crystal structure and microstructure were studied. The annealed powder was characterized using various analytical tools such as TGA, XRD, SEM, and XRF. The results indicate that GaN structure was fully changed to Ga2O3 structure when annealed above 900°C for 2 h. And, as the annealing temperature increased, crystallinity and particle size were enhanced. The increase in particle size of gallium oxide was possibly promoted by powder-sintering which merged particles to larger than 50 nm.
Citations
Flat panel display devices are mainly used as information display devices in the 21st century. The worldwide waste flat panel displays are expected at 2-3 million units but most of them are land-filled for want of a proper recycling technology More specifically, rare earth metals of La and Eu are used as fluorescent materials of Cold Cathode Flourscent Lamp(CCFL)s in the waste flat panel displays and they are critically vulnerable and irreplaceable strategic mineral resources. At present, most of the waste CCFLs are disposed of by land-filling and incineration and proper recovery of 80-plus tons per annum of the rare earth fluorescent materials will significantly contribute to steady supply of them. A dearth of Korean domestic research results on recovery and recycling of rare earth elements in the CCFLs prompts to initiate this status report on overseas research trends and noteworthy research results in related fields.