Process For Recovery Of Metals Research Articles

Roasting-Water Leaching-Slag Cleaning Process for Recovery of Valuable Metals from Li-ion Battery Scrap

Abstract Waste lithium-ion batteries (LIBs) are important secondary sources of valuable materials, including Critical Raw Materials (CRMs) like lithium, cobalt, manganese, and graphite, as defined by the European Union (EU). LIBs also contain nickel and copper, classified as Strategic Raw Materials by the EU since 2023. Significant efforts have been made to develop efficient recycling processes for waste LIBs, with pyrometallurgical processes playing a key role. These technologies are relatively mature, with high adaptability for different raw materials and involve smelting waste batteries above the melting points of battery components, followed by separating metals through reduction reactions. This method efficiently recovers cobalt, copper, and nickel as a metal alloy or matte, while lithium and manganese are lost in the slag phase. The goal of this work was to enhance the recovery of valuable battery metals by combining hydro- and pyrometallurgical processes. Mechanically prepared battery black mass underwent selective sulfation roasting to convert LiCoO2 and Mn-oxides into Li, Co, and Mn sulfates. After roasting, the battery scrap was leached in distilled water at 60 °C, recovering 95% of lithium, 61% of manganese, and 35% of cobalt. The solid leaching residue was then mixed with industrial Ni-slag and biochar. Two experimental series were carried out, one with the addition of industrial Ni-concentrate and one without. The smelting experiments were conducted at 1350 °C in flowing argon atmosphere as a function of time (5–60 min) to investigate the reduction behavior of battery metals. The results show that Co and Ni from the slag and leach residue can be efficiently recovered in the slag cleaning stage. Graphical Abstract

Innovative Process for Strategic Metal Recovery from Electric Arc Furnace Slag by Alkaline Leaching

Innovative Process for Strategic Metal Recovery from Electric Arc Furnace Slag by Alkaline Leaching

Battery Recycling: Policy and Technology Trends

Currently, batteries are used as a promising power source for all industries, and are an essential technology field not only for the industry but also for everyday life. Secondary batteries can be charged or discharged within the allowed range, so they can be used continuously for the life of the battery, and the demand for secondary batteries capable of semi-permanent charging/discharging is increasing through the development of technologies such as IoT, AI, and electric vehicles. In particular, the global electric vehicle conversion speed is very fast, and through this, the spent battery reuse/recycling industry is rapidly growing. The supply chain of the battery market consists of raw materials, materials/parts, products, consumers, and recycling. Along with the increase in demand, the field of waste battery recycling is attracting attention with carbon neutrality, and technology development is being carried out in detail by being divided into areas such as reuse, re-manufacturing, and recycling. Among them, the spent battery reuse/recycling market is expected to grow 19 times from $10.77 billion in 2023 to $208.94 billion in 2040, and battery recycling is emerging as a way to secure a stable supply chain for battery metals as the rapid occurrence of spent batteries is expected.In addition, it is important to strengthen the eco-friendliness of the battery industry due to strengthening global carbon neutrality policies and visualizing climate trade regulations. As the demand for key minerals such as lithium and graphite increase and competition to secure global key minerals is in full swing due to changes in industrial paradigms such as decarbonization/electrification, it is also very important to secure competitiveness in securing key minerals. Resource recovery technology for waste batteries is required to respond to supply chain issues and ESG issues, and the importance of recycling waste batteries is increasing. The waste battery supply market is being formed mainly in the United States, China, and Europe, and among them, the United States and Europe are expected to inevitably switch to an eco-friendly battery reuse/recycling market in terms of intensive environmental regulations and supply chain stabilization. Therefore, it is very necessary to develop next-generation technologies related to the recycling of spent batteries.The waste battery recycling process can be defined as a technology that extracts expensive rare metals from the anode active material of waste batteries. Currently, research and development are being conducted centering on lithium cobalt oxide, a small lithium secondary battery, but it is gradually changing centering on nickel cobalt manganese, a medium and large secondary battery for electric vehicles. The rare metal recovery process is divided into a process of removing and crushing the risk of explosion of a waste battery, which is a pre-treatment process, and recovering the rare metal using a chemical solution, which is a post-treatment process. The post-treatment process has higher technical difficulty, uses a solvent extraction method, and a technology that recovers rare metals such as cobalt and nickel and purifies them to a purity of 99.9% or higher is applied while repeatedly performing the solvent extraction method and electrolytic refining. Advanced technology is being developed to improve the performance of post-treatment technology around the world.Technologies such as reducing the production cost of cathode materials, achieving more than 99% recovery of core metals, and reducing wastewater discharge in spent battery reuse/recycling technologies need to be studied intensively.It is expected to secure a stable rare metal through the recycling of waste batteries, and it will be very important to secure battery resource technology through this.

Innovative Approaches to E-Waste Management: Maximizing Metal Recovery and Sustainable Repurposing of PCB Waste

The global increase in electronic waste (e-waste) necessitates efficient recycling methods to mitigate environmental impact and recover valuable materials. This paper proposes two innovative methodologies for e-waste management, leveraging the strengths of both unorganized and organized sectors. The first method integrates collection, disassembly, and segregation by unorganized units with advanced metal recovery processes by professional recyclers, ensuring maximum yield and minimal environmental harm. The second method focuses on loosening components from PCBs using a combination of chemical and mechanical processes, followed by repurposing shredded PCB pieces into various decorative and household items. This dual approach aims to enhance sustainability, promote eco-friendly practices, and create a profitable business model for e-waste recycling.

Electrochemical Deterioration of a Gold Thin Film in Bicarbonate Solution: Correlative Optical, Nano-Mechanical, and Chemical Considerations.

The electrochemical dissolution of metals in liquid electrolytes is of great concern for various electrochemical technologies. However, it is also the focus for boosting metal recovery processes, e.g., from electronic wastes, one of which is the extraction of gold (Au) using eco-friendly electrolytes. To shed more light on the possibility and improvement of such metal leaching, this work presents the investigation of electrochemical deterioration of a Au nanofilm coated on a silicon (Si) support─ubiquitous materials in electronic components─in aqueous potassium bicarbonate (KHCO3) electrolyte, a solution widely used in food products. In addition to the time-dependent in situ Raman spectra revealing the reduced reflectivity of Au associated with its molecular degradation, the significant role of the electric double layer (EDL) at the metal/electrolyte interface is also indicated. Analyzing surface adhesion maps and force-distance spectra acquired using atomic force microscopy and spectroscopy (AFM/AFS), metal degradation is related to nanoscale worm-shaped reconstructed surface features that act as local sites of reduced refractive index. Complemented by the non-negligible fraction of K observed on the treated Au surfaces using scanning electron microscopy and energy dispersive spectroscopy (SEM/EDS), an electrochemical framework of metal degradation is proposed, depicting the electric-field-induced transport of K+ and H+ ions toward the Au surface regardless of bias polarity and implying the formation of ternary gold hydrides. The consideration of faradic current in the EDL circuit also suggests the occurrence of ternary gold oxides. Such determination is reinforced by the attributability of the polar and electrostatic characteristics of the worm-like features to residual negatively charged anionic clusters of the hydrides and the oxides. The analysis process and the new understanding of metal degradation provide a potential route for inspecting other metal/solution systems.

Sustainable management of end of life crystalline silicon solar panels in Australia: Advancing circular economy practices

The worldwide adaptation of Photovoltaic (PV) technology as a sustainable alternative to fossil fuels, has experienced exponential growth in recent years. However, the lack of effective waste management policies has hindered efficient PV panel disposal and recycling practices. In the absence of effective policies, the worldwide End-of-Life (EoL) PV module accumulation is predicted to reach a critical stage in the early 2030s. This study examines the environmental impacts of different EoL management practices using Life Cycle Assessment (LCA), based on a comprehensive database generated from both literature and industrial data. Five different EoL scenarios were considered for 1000 kg of Crystalline Silicon (c-Si) PV modules with a focus on Australia as a case study, while considering the energy recovery options and emphasizing the economic benefits. From a comprehensive LCA study, it is found that upcycling options reduce the environmental impacts significantly compared to downcycling, while chemical treatment emerges as a preferred option, demonstrating a reduced environmental burden. Nevertheless, the utilization of toxic chemicals during chemical treatment-based PV recycling needs to be reconsidered. Additionally, the usage of chemicals during the metal recovery process of PV module recycling caused the highest environmental burden, necessitating the importance of moving to greener treatment practices. This research study will enable the identification of optimum EoL c-Si module recycling options, contributing to sustainable waste management.

Systematic LCA-AHP Approach to Compare Hydrometallurgical Routes for Copper Recovery from Printed Circuit Boards: Environmental Analysis

To ensure that metal recovery processes in electronic waste are truly sustainable from an industrial perspective, studies on the performance of such methodologies are necessary to verify the economic, environmental, social, and technological viabilities. The importance of conducting multicriteria and comparative investigations into the actual performances of methods used in the recovery of these materials is emphasized, considering trade-offs such as high efficiency in metal extraction balanced against intense consumption of energy and chemical reagents. The analytical hierarchy process, multicriteria decision support tool, and the life cycle assessment tool are proposed to be used in combination in this work to assess and contrast the environmental effects of two hydrometallurgical paths for the recuperation of copper in electronic circuit boards (PCBs). The results indicate that the sulfuric acid method had a copper solubilization efficiency of 90.05%, whereas the route employing the combination of ammonium sulfate and ammonia had an estimated copper solubilization efficacy of 49%. It was feasible to calculate the life cycle effects of the hydrometallurgical procedures connected to the copper recovery activities on the PCBs with regard to the LCA. Compared to the acidic leaching pathway, alkaline leaching was responsible for about 71% of the environmental damage discovered in the study, according to the AHP tool.

Towards circular economy of wasted printed circuit boards of mobile phones fuelled by machine learning and robust mathematical optimization framework

Estimating the operating conditions using conventional process analysis techniques for the maximum metal extraction from the wasted printed circuit boards (WPCB) can provide sub-optimal solutions leading to the low yield of the process. In this paper, we present a closed-loop methodological framework built on machine learning and robust mathematical optimization technique, that offers the mathematical rigour, to determine the optimum operating conditions for the maximum Cu and Ni recovery from the WPCB. Alkali leaching based novel metals recovery process from the WPCB is designed, and the experiments are conducted to collect the data on the percentage recovery of Cu and Ni against the operating levels of the process input variables (ammonia concentration (NH3 conc. (g/L)), ammonium sulfate concentration ((NH4)2SO4 conc. (g/L)), H2O2 concentration (H2O2 conc. (M)), time (h), liquid to solid ratio (L/S ratio, (mL/g)), temperature (Temp. (°C)), and stirring speed (rpm)). The experimental data is deployed to construct the functional mapping between the nonlinear output variables of metals recovery process with the hyperdimensional input space through artificial neural network (ANN) based modelling algorithm – a powerful universal function approximator. Well-predictive ANN models for Cu and Ni recovery are developed having co-efficient of determination (R2) value more than 0.90. Partial derivative-based sensitivity analysis is then carried out to establish the order of the significance of the input variables that is backed by the domain knowledge, thus promotes the interpretability of the trained ANN models. The hybridization of ANN with NLP (nonlinear programming) framework is implemented for the determination of optimized operating conditions to extract maximum Cu and Ni under separate and combined model of metal extraction. The robustness of the determined solutions is verified, the determined optimized solutions for the metal recovery are validated in the lab, and the maximum metal recovery, i.e., 100 % Cu and 90 % Ni is extracted from the WPCB. This research demonstrates the effective utilization of ANN model-based robust optimization approach for the metal recovery from the WPCB that supports the circular economy for the metal extraction industry.

OREATE as a High Yield and Purity Electrochemical Process for Transition and Rare Earth Metal Recovery

Developing a process that can consistently convert transition and rare earth metal oxides to chemically pure metals in near quantitative yield will have significant impact in many levels, from fundamental science to national security-related applications. Traditional separation methods of lanthanides and actinides from aqueous media have been based on liquid-liquid extractions that have proven to be quite efficient, though they are expensive and require complex engineering. Likewise, separation by pyro-chemistry provides a good recovery performance but requires the use of high temperatures that adds technological difficulties to the process. An alternative method that has grown interest in the last few years is the utilization of the difference in the metals’ reduction potentials from ionic state to metallic state. However, this electrochemical approach requires more negative reduction potentials than hydrogen evolution, which requires a very challenging control of their electrolytic deposition onto solid cathodes.In recent years, our team at LANL has been working on the development of OREATE (Oxide Reduction by Electrochemical Amalgamation and Thermal Extraction). OREATE is a holistic electrochemical approach that involves an initial step wherein the metal oxide is dissolved and chlorinated into an acidic medium. The dissolved metal cation is then electrochemically amalgamated via reduction using a mercury pool cathode. Finally, mercury's high vapor pressure allows an easy thermal extraction process to obtain the metal. From the conceptual perspective and preliminary results, the OREATE process appears easier and simpler than traditional separation methods and is suitable for small- and large-scale preparation of high purity metals.The results obtained using Cerium (Ce) as a surrogate metal demonstrated near quantitative yield of the electrochemical amalgamation (yield > 99%), almost complete mercury recovery during the thermal extraction (Hg recovery > 99.5%), and high purity of the Ce metal product (purity > 99%). Moreover, a variety of system parameters such as the pH of the buffered solution, concentration of cerium, reduction potential, and temperature were explored to evaluate the effect that the scaling up of the OREATE process may have on reaction rate, current efficiency, process yield, and temperature management.

Design and Production of Functionalized Electrospun Fibers for Palladium Recovery.

Adsorption stands out as a leading wastewater treatment method for ion removal or recovery. Polymeric fibers, notably electrospun ones, are gaining prominence due to their high capacity and easy recovery. Electrospinning offers a cost-effective means to produce fibers with a large surface area and high adsorption capacity. These fibers can be further functionalized with chemical substances acting as specific ligands for metal ions, bolstering their adsorption capabilities. In this study, dithioester-functionalized electrospun fibers were synthesized as an alternative to conventional sorbents for palladium recovery from acidic chloride solutions, similar to those used in hydrometallurgical processes for platinum group metal recovery (Pd, Pt, Rh···) from spent catalysts. Fibers with identical chemical composition but varying morphology were examined to assess their impact on palladium adsorption efficiency (i.e., beads-free and beads-on-string morphologies). Experimental investigations involved model solutions with varying palladium concentration, temperature, acidity (adjusted with HCl content), and salinity (adjusted with NaCl), utilizing both pure and dithioester-functionalized fibers. Experimental results demonstrate enhanced adsorption efficiency at lower temperatures and in 0.1 M HCl, with a negligible influence from solution salinity. Moreover, both pure polymeric and dithioester-functionalized electrospun fibers exhibit highly efficient palladium recovery. Furthermore, under optimal conditions, starting from an 80 mg/L palladium solution, a 95% recovery of palladium can be achieved with a sorbent dosage below 4 g/L of functionalized electrospun fibers. The adsorption data are well described by the Langmuir isotherm model for the pure polymeric fibers. At the same time, the contribution of dithioesters has been separately accounted for to describe the behavior of functionalized electrospun fibers. Thermal recovery of palladium from the spent sorbents has also been investigated.

Recent and Novel Leaching Processes for Recovery of Metals from Spent Lithium-ion Batteries: A Review

Recent and Novel Leaching Processes for Recovery of Metals from Spent Lithium-ion Batteries: A Review

Tailoring the Use of 8-Hydroxyquinolines for the Facile Separation of Iron, Dysprosium and Neodymium.

Permanent magnets (PMs) containing rare earth elements (REEs) can generate energy in a sustainable manner. With an anticipated tenfold increase in REEs demand by 2050, one of the crucial strategies to meet the demand is developing of efficient recycling methods. NdFeB PMs are the most widely employed, however, the similar chemical properties of Nd (20-30 % wt.) and Dy (0-10 % wt.) make their recycling challenging, but possible using appropriate ligands. In this work, we investigated commercially available 8-hydroxyquinolines (HQs) as potential Fe/Nd/Dy complexing agents enabling metal separation by selective precipitation playing on specific structure/property (solubility) relationship. Specifically, test ethanolic solutions of nitrate salts, prepared to mimic the main components of a PM leachate, were treated with functionalized HQs. We demonstrated that Fe3+ can be separated as insoluble [Fe(QCl,I)3] from soluble [REE(QCl,I)4]- complexes (QCl,I -: 5-Cl-7-I-8-hydoxyquinolinate). Following that, QCl - (5-Cl-8-hydroxyquinolinate) formed insoluble [Nd3(QCl)9] and soluble (Bu4N)[Dy(QCl)4]. The process ultimately gave a solution phase containing Dy with only traces of Nd. In a preliminary attempt to assess the potentiality of a low environmental impact process, REEs were recovered as oxalates, while the ligands as well as Bu4N+ ions, were regenerated and internally reused, thus contributing to the sustainability of a possible metal recovery process.

Efficient recovery of all valuable metals from spent HDS catalysts: Based on roasting mechanisms for enhanced selective leaching and separation

Recovery of all valuable metals such as Ni, Mo, V and Al from spent hydrodesulfurization (HDS) catalysts is beneficial to environmental protection and resource recycling. The current recycling process mostly considers the recovery of Mo and V than recovery of Ni and Al, and generates a large amount of difficult-to-decompose Ni-Al residue and wastewater. Aiming at the insufficiency of the current recycling process, in this study, a novel pyro-hydrometallurgical process for efficient and complete recovery of metals from spent HDS catalysts was proposed. The mechanisms of phase transformation during roasting and leaching are investigated by XRD, XPS and SEM in depth. The modulation of the phase transformation of the spent HDS catalyst in the oxidative roasting process is the key to the influence on the leaching of Ni and Al. Inhibition of θ-Al2O3 phase and Ni-Al spinel generation by controlled roasting can achieve efficient leaching of Mo, V, Ni and Al. Subsequently, Mo and V were selectively leached with 2 mol/L Na2CO3, and the alkaline leach residue obtained was treated with 6 mol/L HCl. The results showed that alkaline leaching efficiencies of Mo and V reached 99.73 % and 91.86 % while acid leaching efficiencies of Ni and Al reached 99.71 % and 90.27 %, respectively. The metals of acid leach solution were recovered by using N235, HBL110 and NaAlO2 stepwise. This new process has the advantages of high efficiency and comprehensive metal recovery, high product purity, and low amount of slag and wastewater, and has good prospects for industrial application.

Towards Integration of Ni-Slag Cleaning Process and Lithium-Ion Battery Recycling for an Efficient Recovery of Valuable Metals

Spent lithium-ion batteries (SBs) are important sources of valuable and critical raw materials. An integration of battery recycling with well-established primary processes for metals production has many advantages. In this work, the recycling of two battery scrap fractions obtained from mechanical pretreatment was integrated with a Ni-slag cleaning process at laboratory scale. Graphite from SBs acted as the main reductant, and the reduction behavior of major and trace elements was investigated as a function of time at 1350 °C. Major CO and CO2 concentrations, as well as minor amounts of SO2, NO2, CH4, and C2H4, were detected in the off-gas line. The evolution of gases took place within the first minutes of the experiments, which indicated that metal oxide reduction reactions as well as decomposition of the organic binders both happened very rapidly. This result is in line with the analytical results obtained for the slag phase, where the most significant metal oxide reduction was observed to take place within the first 5 to 10 minutes of the experiments. The distribution coefficient values for Co and Ni between metal alloy and slag as well as between matte and slag showed no significant differences when battery scrap fractions with different compositions were used. The addition of Ni-concentrate in the starting mixture resulted in increasing recoveries of Ni and Co, as well as improved settling of the matte phase.

Radiation Techniques for Tracking the Progress of the Hydrometallurgical Leaching Process: A Case Study of Mn and Zn

With advancements in hardware and software, non-destructive radiometric analytical methods have become popular in a wide range of applications. A typical case is the study of the leaching process of metals from mineral ores and mine tailings. The objective of the current study was to develop a radiometric method based on neutron activation analysis (NAA), in particular, delayed gamma neutron activation analysis (DGNAA), to monitor the process of Mn and Zn leaching from Ti ore, Cu mine tailings, and Zn-Pb mine tailings. The DGNAA method was performed using a neutron source: a deuterium-tritium (D-T) neutron generator for Mn and a MARIA research nuclear reactor for Zn. Laboratory-scale Mn leaching from Ti ores, Cu tailings, and Zn-Pb tailings was investigated using delayed gamma-rays of 56Mn (half-life of 2.6 h). The dissolution efficiencies of Mn were found to increase with interaction time and HCl concentration (1 to 5 M) and to vary with the leaching temperature (22.5 to 110 °C). Such results were found to agree with those obtained by total reflection X-ray fluorescence (TXRF) spectrometry for the same samples. 65Zn (half-life of 244 days) was chosen to investigate real-time/online leaching of Zn in Ti ore, Cu tailings, and Zn-Pb tailings. During online monitoring, Zn recovery was also reported to increase with increased leaching time. After approximately 300 min of leaching, 80%, 79%, and 53% recovery of Zn in Zn-Pb tailings, Ti ore, and Cu tailings, respectively, were reported. Theoretically, developed mathematical prediction models for 65Zn radiotracer analysis showed that the spherical diffusion model requires much less time to attain saturation compared to the linear diffusion model. The results of NAA for Zn were compared with those obtained by handheld X-ray fluorescence (handheld-XRF) and TXRF analysis. The analyzed samples encompassed leached Ti ore, Cu tailings, and Zn-Pb tailings which were subjected to different conditions of leaching time, temperature, and HCl concentrations. The XRF analysis confirmed that the leaching efficiencies of Zn rise with the increase in leaching time and HCl concentration and fluctuate with leaching temperature. The developed approach is important and can be applied in laboratories and industrial setups for online monitoring of the recovery of any element whose isotopes can be activated using neutrons. The efficiency of the metal-recovery process has a direct impact on the normal operation and economic advantages of hydrometallurgy.

A tandem approach for precipitant-free highly selective recovery of valuable metals from end-of-life lithium-ion batteries using a green deep eutectic solvent

Recently, recycling lithium-ion batteries (LIBs) waste and the efficient recovery of valuable metals has become crucial for the circular economy. Deep eutectic solvents (DESs) have shown immense potential for metal extraction from end-of-life (EoL) LIBs. However, a complicated subsequent separation process is required due to the non-selectivity of the DES components for metal. Herein, we propose a tandem precipitant-free hydrometallurgical process for the selective recovery of Li and other valuable metals (Ni, Co, Mn) from EoL LIBs using a green DES. The process parameters, viz., reaction temperature (T), time (t), pulp density (S/L), and molar ratio (MR) of ethylene glycol to tartaric acid, were optimized via the statistical optimization technique of response surface methodology. The results revealed maximum extraction efficiencies of 99.2 ± 0.5%, 96.1 ± 1.4%, 95.2 ± 1.2%, and 97.8 ± 1.5% for Li, Ni, Co, and Mn, respectively, under the optimized process conditions of T = 118 °C, t = 17 min, S/L = 42 g/L, and MR = 3:1. The kinetic study showed that interfacial reaction governed the extraction process. A plausible mechanism depicting the role of DES constituents in synergistically facilitating the extraction reaction was elucidated. Moreover, Li and other metals (Ni, Co, and Mn) were selectively separated and recovered with an overall efficiency of ∼99%. The reusability of the recovered metal products and the DES were also assessed for a closed-loop recycling process. At the outset, the proposed process paves the way for a greener alternative for recycling valuable metals from EoL LIBs rather than conventional acid-based leaching processes.

Comparative life cycle assessment of copper and gold recovery from waste printed circuit boards: Pyrometallurgy, chemical leaching and bioleaching

Printed circuit boards (PCBs) make up a substantial amount of electronic waste (e-waste) generated annually. Waste PCBs contain high quantities of copper and gold in comparison to natural ores. As such, “urban mining” of waste PCBs to recover these metals is of commercial interest. In this work, we used life cycle assessment to compare the environmental impact of four copper and gold recovery processes. We evaluated pyrometallurgy, chemical leaching, and bioleaching, as well as a hybrid leaching process that uses bioleaching to recover copper and chemical leaching to recover gold. Furthermore, we considered differences in environmental impact based on differences in electricity sources. If electricity comes from fossil fuels, the pyrometallurgical process results in the lowest environmental impact in all impact categories studied. If electricity comes from carbon-free sources, the pyrometallurgical process results in the lowest environmental impact in all categories studied except global warming, where the hybrid leaching process results in the lowest impact. In all cases, metal recovery from waste PCBs leads to lower environmental impact than primary metal production. Our goal is to guide e-waste recyclers towards more environmentally sustainable metal recovery processes and to provide knowledge gaps in the field to guide future research.

Mechanism of highly efficient oil removal from spent hydrodesulfurization catalysts by ultrasound-assisted surfactant cleaning methods

The removal of crude oil from spent hydrodesulfurization catalysts constitutes the preliminary stage in the recovery process of valuable metals. However, the traditional roasting method for the removal exhibits massive limitations. In view of this, the present study used an ultrasound-assisted surfactant cleaning method to remove crude oil from spent hydrodesulfurization catalysts, which demonstrated effectiveness. Furthermore, the study investigated the mechanism governing the process with calculation and experiments, so as to provide a comprehensive understanding of the cleaning method’s efficacy. The surfactant selection was predicated on the performance in the IFT test, with SDBS and TX-100 finally being chosen. Subsequent calculations and analysis were then conducted to elucidate their frontier molecular orbitals, electrostatic potential, and polarity. It has been found that both SDBS and TX-100 possess the smallest LUMO-HOMO energy gap (ΔE), registering at 4.91 eV and 4.80 eV, respectively, and presenting the highest interfacial reactivity. The hydrophilic structure in the surfactant regulates the wettability of the oil-water interface, and the long-chain alkanes have excellent non-polar properties that promote the dissolution of crude oil. The ultrasonic-assisted process further improves the interface properties and enhances the oil removal effect. Surprisingly, the crude oil residue was reduced to 0.25% under optimal conditions. The final phase entailed the techno-economic evaluation of the entire process, revealing that, in comparison to the roasting method, this process saves $0.38 per kilogram of spent HDS catalyst, with the advantages of operational simplicity and emission-free. Generally, this study shed new light on the realization of efficient oil removal, with the salience of green, sustainable, and economical.

Complete recovery of valuable metals from chlorinated titanium-white waste acids: Focus on solvent extraction for recovery and preparation of battery-grade manganese sulfate (MnSO4·H2O) from lab to pilot scale

Chlorination titanium-white waste acid (CTWA) is known to contain a substantial number of valuable metals, including Mn, which can be utilized in the manufacturing of high-value battery cathode materials. Based on the concept of complete resource recovery and zero pollution, a novel process for metal recovery from CTWA has been developed. D2EHPA was used to extract Sc, V from CTWA. Al was completely removed by slowly adding 1.5 mol/L NaOH until the solution pH reached 4.20 and stabilized for 0.5 h. This process resulted in a limited loss of 11 % for Fe and 5 % for Mn. An oxidative precipitation method was proposed to process the Al-free solution to preparate a pure and easily filterable FePO4 product, which can be used in the production of battery materials. Additionally, the loss of Mn in this process was less than 0.5 %. After removing Fe and Al, the pre-extraction feed has an O/A ratio of 2.5:1, a temperature of 40 °C, and an equilibrium pH of 4.5 ∼ 5.0, it is possible to extract Mn at over 99.50 % using a 5-stage extraction. The loaded phase is scrubbed with 5 g/L H2SO4, O/A = 5:1. It is then cyclically stripped with 75 g/L H2SO4, O/A = 8:1, to obtain a battery-grade MnSO4 solution. The stripped solution can be 100 % crystallized to obtain battery-grade MnSO4·H2O products after removing heavy metals using BaS and removing oil with activated carbon. The recovery of Mn in the extraction process was 97.59 %. The pilot test was conducted to demonstrate that the extraction process can be efficiently and continuously produced. The process achieved the recovery of valuable metals from CTWA and the preparation of corresponding products. This process is comprehensive and environmentally friendly, which has an industrial foundation.

Implementing a sustainable process for the recovery of palladium from spent catalysts at industrial scale: A LCA approach

Due to its unique physicochemical properties, palladium is widely used in several industry applications (e.g., vehicle emission control). In view of the circular economy, it is essential to explore secondary sources of palladium, such as urban mines. Current technologies for effective palladium recovery involve high energy consumption and severe environmental impact. More recently, a novel green method for recovering palladium from spent catalysts through a combination of mild acidic leaching and photodeposition on ZnO nanoparticles was proposed on a laboratory scale. In the present study, the environmental impacts of this recovery method, properly upscaled and modelled, was assessed by employing the LCA approach. Specifically, a comparative LCA was carried out for the process with as well as without recycling key components, such as Cu (II) and NaCl for the leaching solution and ZnO. The outcomes identified critical areas and drove the investigation of alternative process configurations to reduce its environmental footprint, such as the use of carbon dioxide in the photodeposition process with the aim of decreasing the resulting terrestrial ecotoxicity. This study marks a significant step forward in advancing research toward industrial−scale implementation of palladium recovery. It provides valuable insights for researchers in the field of green physicochemical processes for metal recovery, thus offering guidance for future decision−making towards more sustainable practices.