Pub Date : 2025-06-25DOI: 10.1016/j.hydromet.2025.106526
Nikita A. Milevskii, Dmitriy V. Lobovich, Arina V. Milevskaya, Yulia A. Zakhodyaeva, Andrey A. Voshkin
Hydrophobic deep eutectic solvents (HDES) have long been used for the extraction of metal ions from aqueous systems. This study proposes the use of HDES composed of dodecanoic acid and menthol as a diluent for tributyl phosphate (TBP), which serves as the extractant. The results demonstrate that the extraction system developed remains stable across a broad range of TBP concentrations and possesses excellent physical properties, making it suitable for laboratory-scale extraction equipment. By examining the extraction of iron and titanium ions, key dependencies of extraction efficiency were identified as varying acidity levels, volume ratios, initial metal concentrations and conditions for effective stripping. Notably, the efficiency of the extractant remained unchanged after ten cycles of extraction and stripping, particularly for titanium ions extracted from 10 mol/L hydrochloric acid. This indicates the chemical stability of the proposed extraction system. A continuous separation process for iron and titanium was successfully implemented on laboratory extraction equipment using liquid pseudomembranes, achieving an efficiency greater than 95 % of the theoretical maximum. These findings suggest that HDES have significant potential for use as non-volatile, non-combustible and renewable solvents in extraction processes.
{"title":"The use of hydrophobic deep eutectic solvent dodecanoic acid/menthol as a sustainable diluent for the continuous extraction process of Fe and Ti separation","authors":"Nikita A. Milevskii, Dmitriy V. Lobovich, Arina V. Milevskaya, Yulia A. Zakhodyaeva, Andrey A. Voshkin","doi":"10.1016/j.hydromet.2025.106526","DOIUrl":"10.1016/j.hydromet.2025.106526","url":null,"abstract":"<div><div>Hydrophobic deep eutectic solvents (HDES) have long been used for the extraction of metal ions from aqueous systems. This study proposes the use of HDES composed of dodecanoic acid and menthol as a diluent for tributyl phosphate (TBP), which serves as the extractant. The results demonstrate that the extraction system developed remains stable across a broad range of TBP concentrations and possesses excellent physical properties, making it suitable for laboratory-scale extraction equipment. By examining the extraction of iron and titanium ions, key dependencies of extraction efficiency were identified as varying acidity levels, volume ratios, initial metal concentrations and conditions for effective stripping. Notably, the efficiency of the extractant remained unchanged after ten cycles of extraction and stripping, particularly for titanium ions extracted from 10 mol/L hydrochloric acid. This indicates the chemical stability of the proposed extraction system. A continuous separation process for iron and titanium was successfully implemented on laboratory extraction equipment using liquid pseudomembranes, achieving an efficiency greater than 95 % of the theoretical maximum. These findings suggest that HDES have significant potential for use as non-volatile, non-combustible and renewable solvents in extraction processes.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106526"},"PeriodicalIF":4.8,"publicationDate":"2025-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144490604","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-06-25DOI: 10.1016/j.hydromet.2025.106528
Cecilia Daniela Costa , María José Hernandez Triana , Mario Avila , Virginia Emilse Diz , Graciela Alicia González
The cementation of copper on aluminium is a well-studied process, typically facilitated by chloride ions to overcome the insulating aluminium oxide layer. This study presents an alternative approach using magnetite (Fe₃O₄) nanoparticles as electron (redox) mediators, allowing the cementation process to occur despite the presence of the aluminium oxide layer. After optimizing the concentration of the Fe₃O₄ suspension, the pH, and the reaction time, the performance of this method was compared to the classical chloride ion-based approach. The nanoparticle assisted method achieved higher recovery (%) of copper, but at a slower pace. This difference in reaction speed explains the more compact, non-oxidize copper deposits observed by SEM and DRX, in contrast to the dendritic and airy deposits with a high fraction of Cu₂O obtained using the classical chloride method. Under optimized conditions, the method was applied for the recovery of Cu from two industrial PCB solutions, achieving excellent recoveries after adjusting the pH.
{"title":"Evaluating the effectiveness of iron oxide (Fe3O4) nanoparticles vs. traditional chloride methods for copper cementation and recovery from industrial waste solutions by aluminium","authors":"Cecilia Daniela Costa , María José Hernandez Triana , Mario Avila , Virginia Emilse Diz , Graciela Alicia González","doi":"10.1016/j.hydromet.2025.106528","DOIUrl":"10.1016/j.hydromet.2025.106528","url":null,"abstract":"<div><div>The cementation of copper on aluminium is a well-studied process, typically facilitated by chloride ions to overcome the insulating aluminium oxide layer. This study presents an alternative approach using magnetite (Fe₃O₄) nanoparticles as electron (redox) mediators, allowing the cementation process to occur despite the presence of the aluminium oxide layer. After optimizing the concentration of the Fe₃O₄ suspension, the pH, and the reaction time, the performance of this method was compared to the classical chloride ion-based approach. The nanoparticle assisted method achieved higher recovery (%) of copper, but at a slower pace. This difference in reaction speed explains the more compact, non-oxidize copper deposits observed by SEM and DRX, in contrast to the dendritic and airy deposits with a high fraction of Cu₂O obtained using the classical chloride method. Under optimized conditions, the method was applied for the recovery of Cu from two industrial PCB solutions, achieving excellent recoveries after adjusting the pH.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106528"},"PeriodicalIF":4.8,"publicationDate":"2025-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144501080","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-06-24DOI: 10.1016/j.hydromet.2025.106524
Qiaofa Lan , Xiaolin Zhang , Fei Niu , Donghui Liu , Youming Yang
Ionic rare earth purification residue (PR) originates from refining of ionic rare earth ores and is predominantly composed of rare earth elements (REEs), aluminum (Al), and silicon (Si). This is a recyclable secondary resource. It provides substantial challenges due to its classification as low-level radioactive waste (LLW). Recognizing the distinctive properties of PR, this paper describes a highly efficient process for the recovery and enrichment of Al, REEs, uranium (U), and thorium (Th) through a multistep process encompassing alkali digestion, hydrochloric acid leaching, sole extractant enrichment and separation. At a controlled temperature of 70 °C, the Al digestion efficiency reached 88.9 %. The alkali digestion residue underwent hydrochloric acid leaching, yielding leaching efficiencies of 99.9 %, 99.4 %, and 99.0 % for REEs, U(VI), and Th(IV), respectively. Notably, the amount of insoluble residue was reduced by 90 %, and it was transformed from LLW into general solid waste residue. Additionally, the utilization of 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester (HEHEHP) as the sole extractant provided 100 % extraction efficiencies for U(VI) and Th(IV). After stepwise stripping processes, the purities of both U(VI) and Th(IV) exceeded 90 %. The REEs were precipitated as RE2(C2O4)3 and subsequently calcined to produce rare earth oxides with a recovery of 90.1 % and a purity of 97.4 %. This comprehensive scheme addressed the persistent challenges associated with long-term storage and radiological environmental risk.
{"title":"Recovery process of rare earths, Al, U, and Th from ionic rare earth purification residue using sequential alkaline leaching, acid leaching solvent extraction and stripping","authors":"Qiaofa Lan , Xiaolin Zhang , Fei Niu , Donghui Liu , Youming Yang","doi":"10.1016/j.hydromet.2025.106524","DOIUrl":"10.1016/j.hydromet.2025.106524","url":null,"abstract":"<div><div>Ionic rare earth purification residue (PR) originates from refining of ionic rare earth ores and is predominantly composed of rare earth elements (REEs), aluminum (Al), and silicon (Si). This is a recyclable secondary resource. It provides substantial challenges due to its classification as low-level radioactive waste (LLW). Recognizing the distinctive properties of PR, this paper describes a highly efficient process for the recovery and enrichment of Al, REEs, uranium (U), and thorium (Th) through a multistep process encompassing alkali digestion, hydrochloric acid leaching, sole extractant enrichment and separation. At a controlled temperature of 70 °C, the Al digestion efficiency reached 88.9 %. The alkali digestion residue underwent hydrochloric acid leaching, yielding leaching efficiencies of 99.9 %, 99.4 %, and 99.0 % for REEs, U(VI), and Th(IV), respectively. Notably, the amount of insoluble residue was reduced by 90 %, and it was transformed from LLW into general solid waste residue. Additionally, the utilization of 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester (HEHEHP) as the sole extractant provided 100 % extraction efficiencies for U(VI) and Th(IV). After stepwise stripping processes, the purities of both U(VI) and Th(IV) exceeded 90 %. The REEs were precipitated as RE<sub>2</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub> and subsequently calcined to produce rare earth oxides with a recovery of 90.1 % and a purity of 97.4 %. This comprehensive scheme addressed the persistent challenges associated with long-term storage and radiological environmental risk.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106524"},"PeriodicalIF":4.8,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144518263","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-06-24DOI: 10.1016/j.hydromet.2025.106525
Jingzheng Wang , Hongxiang Xu , Yijun Cao , Kejia Ning , Biao Fu , Lin Ma , Xin Sun , Yuntao Kang , Mengting Hong , Guixia Fan , Xiahui Gui , Jiushuai Deng
Coal resources are a potential source of strategic metals. This study explores the leaching characteristics and mechanisms for extracting gallium (Ga), lithium (Li), and rare earth elements (REEs) from coal gangue under roasting and acid leaching conditions. Based on the differences in their leaching characteristics, a stepwise leaching strategy is proposed for efficient separation and recovery. Gallium and lithium are primarily associated with silicate minerals, while rare earth elements exist as independent rare earth minerals. Roasting at 600 °C enhances chemical reactivity, increasing the specific surface area and pore volume of the sample, thereby improving the leaching efficiency of Ga, Li, and REEs. The leaching of Ga and Li is mainly controlled by chemical reactions and is highly temperature-dependent, while the leaching of REEs follows a mixed control model. The stepwise extraction strategy involves leaching at 50 °C for 15 min to recover approximately 80 % of the REEs, with minimal loss of Ga and Li (∼7 %), followed by further leaching at 90 °C for 180 min to recover the remaining Ga and Li. This process demonstrates the potential of the stepwise extraction strategy for the efficient separation and recovery of these elements.
{"title":"Stepwise recovery of gallium (Ga), lithium (Li), and rare earth elements (REEs) from roasted coal gangue based on leaching kinetics differentiation","authors":"Jingzheng Wang , Hongxiang Xu , Yijun Cao , Kejia Ning , Biao Fu , Lin Ma , Xin Sun , Yuntao Kang , Mengting Hong , Guixia Fan , Xiahui Gui , Jiushuai Deng","doi":"10.1016/j.hydromet.2025.106525","DOIUrl":"10.1016/j.hydromet.2025.106525","url":null,"abstract":"<div><div>Coal resources are a potential source of strategic metals. This study explores the leaching characteristics and mechanisms for extracting gallium (Ga), lithium (Li), and rare earth elements (REEs) from coal gangue under roasting and acid leaching conditions. Based on the differences in their leaching characteristics, a stepwise leaching strategy is proposed for efficient separation and recovery. Gallium and lithium are primarily associated with silicate minerals, while rare earth elements exist as independent rare earth minerals. Roasting at 600 °C enhances chemical reactivity, increasing the specific surface area and pore volume of the sample, thereby improving the leaching efficiency of Ga, Li, and REEs. The leaching of Ga and Li is mainly controlled by chemical reactions and is highly temperature-dependent, while the leaching of REEs follows a mixed control model. The stepwise extraction strategy involves leaching at 50 °C for 15 min to recover approximately 80 % of the REEs, with minimal loss of Ga and Li (∼7 %), followed by further leaching at 90 °C for 180 min to recover the remaining Ga and Li. This process demonstrates the potential of the stepwise extraction strategy for the efficient separation and recovery of these elements.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106525"},"PeriodicalIF":4.8,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144501081","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-06-16DOI: 10.1016/j.hydromet.2025.106519
Kuifang Zhang , Bohan Wei , Bin Zeng , Sen Qiu , Xiaocong Zhong , Ruixiang Wang
Sulfate leachate from spent ternary lithium-ion batteries (LIBs) contain valuable metals, such as transition metals (Ni, Co, and Mn) and Li, and impurity metals, such as Al and Fe. Selectively separating them from solutions is necessary for their recovery. In this work, a stepwise solvent extraction and precipitation process is proposed for the selective separation and recovery of transition metals (Ni, Co, and Mn) and Li from sulfate-leaching solutions of spent ternary lithium-ion batteries. First, 100 % of the impurity metals (Al and Fe) were selectively removed from the solution through a single-stage extraction using 22.5 % (v/v) N1923 in sulfonated kerosene at an O/A ratio of 1:1 for 10 min. The losses of the transition metals (Ni, Co, and Mn) and Li were only 1.65 %. The Al and Fe in the loaded organic system was completely stripped using a 1 mol/L HNO3 solution, followed by regeneration with sodium carbonate solution. Subsequently, the raffinate (pH = 4.46) was directly used for the co-extraction of Ni, Co, and Mn by Cyanex 272. A five-stage countercurrent extraction was performed with an organic system consisting of 1 mol/L Cyanex 272 (saponification degree: 50 %) in sulfonated kerosene, using an O/A ratio of 2.25:1. Nearly all of the Ni, Co, and Mn were extracted, while only 1.43 % Li was co-extracted. The extracted Ni, Co, and Mn in the loaded organic system were completely stripped through five-stage counter-current stripping using 1 mol/L H2SO4 with an O/A ratio of 5:1. During the stepwise solvent extraction process, stripped solutions of Ni, Co, Mn, and Li raffinates were sent to precipitate the pure ternary material precursors and Li2CO3. This study introduces a novel method for recycling spent ternary lithium-ion batteries.
{"title":"Recovery of transition metals (Ni, Co, and Mn) and Li from the sulfate leach solutions of spent ternary lithium-ion batteries by stepwise solvent extraction and precipitation","authors":"Kuifang Zhang , Bohan Wei , Bin Zeng , Sen Qiu , Xiaocong Zhong , Ruixiang Wang","doi":"10.1016/j.hydromet.2025.106519","DOIUrl":"10.1016/j.hydromet.2025.106519","url":null,"abstract":"<div><div>Sulfate leachate from spent ternary lithium-ion batteries (LIBs) contain valuable metals, such as transition metals (Ni, Co, and Mn) and Li, and impurity metals, such as Al and Fe. Selectively separating them from solutions is necessary for their recovery. In this work, a stepwise solvent extraction and precipitation process is proposed for the selective separation and recovery of transition metals (Ni, Co, and Mn) and Li from sulfate-leaching solutions of spent ternary lithium-ion batteries. First, 100 % of the impurity metals (Al and Fe) were selectively removed from the solution through a single-stage extraction using 22.5 % (<em>v</em>/v) N1923 in sulfonated kerosene at an O/A ratio of 1:1 for 10 min. The losses of the transition metals (Ni, Co, and Mn) and Li were only 1.65 %. The Al and Fe in the loaded organic system was completely stripped using a 1 mol/L HNO<sub>3</sub> solution, followed by regeneration with sodium carbonate solution. Subsequently, the raffinate (pH = 4.46) was directly used for the co-extraction of Ni, Co, and Mn by Cyanex 272. A five-stage countercurrent extraction was performed with an organic system consisting of 1 mol/L Cyanex 272 (saponification degree: 50 %) in sulfonated kerosene, using an O/A ratio of 2.25:1. Nearly all of the Ni, Co, and Mn were extracted, while only 1.43 % Li was co-extracted. The extracted Ni, Co, and Mn in the loaded organic system were completely stripped through five-stage counter-current stripping using 1 mol/L H<sub>2</sub>SO<sub>4</sub> with an O/A ratio of 5:1. During the stepwise solvent extraction process, stripped solutions of Ni, Co, Mn, and Li raffinates were sent to precipitate the pure ternary material precursors and Li<sub>2</sub>CO<sub>3</sub>. This study introduces a novel method for recycling spent ternary lithium-ion batteries.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106519"},"PeriodicalIF":4.8,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144321257","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-06-16DOI: 10.1016/j.hydromet.2025.106516
Junghyun Lim , Yunjai Jang , Junbeum Lee , Chaehyeon Lee , Omayma Jbari , Kyungjung Kwon , Eunhyea Chung
The rapid increase in lithium-ion batteries (LIBs) usage, particularly in portable electronics and electric vehicles, has led to considerable environmental challenges due to waste generation, creating a need for recovery of metals from waste. This review examines methods for recovering valuable metals—Co, Ni, Mn, and Li—from the leachates of end-of-life spent LIBs using hydrometallurgical unit processes, summarizing current research and technological advancements. Recovery techniques such as precipitation, solvent extraction, electrodeposition, ion exchange (and adsorption), and other approaches were evaluated in terms of efficiency, cost-effectiveness, and environmental impact. Moreover, a cost analysis comparing hydrometallurgical methods—precipitation, solvent extraction, electrochemical extraction—was conducted. This review highlights the technological gaps in current recovery methods and stresses the need for further research to improve metal recoveries and minimize the environmental impacts of hydrometallurgical processes. Integrating experimental findings, the review offers a comprehensive overview of recovery pathways and provides insights into the future of sustainable LIBs recycling and cost analysis.
{"title":"Hydrometallurgical process of spent lithium-ion battery recycling Part. 2 Recovery of valuable metals from the cathode active material leachates: Review and cost analysis","authors":"Junghyun Lim , Yunjai Jang , Junbeum Lee , Chaehyeon Lee , Omayma Jbari , Kyungjung Kwon , Eunhyea Chung","doi":"10.1016/j.hydromet.2025.106516","DOIUrl":"10.1016/j.hydromet.2025.106516","url":null,"abstract":"<div><div>The rapid increase in lithium-ion batteries (LIBs) usage, particularly in portable electronics and electric vehicles, has led to considerable environmental challenges due to waste generation, creating a need for recovery of metals from waste. This review examines methods for recovering valuable metals—Co, Ni, Mn, and Li—from the leachates of end-of-life spent LIBs using hydrometallurgical unit processes, summarizing current research and technological advancements. Recovery techniques such as precipitation, solvent extraction, electrodeposition, ion exchange (and adsorption), and other approaches were evaluated in terms of efficiency, cost-effectiveness, and environmental impact. Moreover, a cost analysis comparing hydrometallurgical methods—precipitation, solvent extraction, electrochemical extraction—was conducted. This review highlights the technological gaps in current recovery methods and stresses the need for further research to improve metal recoveries and minimize the environmental impacts of hydrometallurgical processes. Integrating experimental findings, the review offers a comprehensive overview of recovery pathways and provides insights into the future of sustainable LIBs recycling and cost analysis.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106516"},"PeriodicalIF":4.8,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144313460","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-06-16DOI: 10.1016/j.hydromet.2025.106520
Yifan Wang , Yonghui Song , Xinwei Zhang , Ping Dong , Ning Yin , Zeyu Wang , Shilei Lang
This study prepared a novel adsorption material XAD-2-HDES with fast adsorption rate by impregnating XAD-2 resin with quaternary ammonium hydrophobic deep eutectic solvent (HDES). It was applied to the enrichment and recovery of various precious metal ions in aqua regia solution. The results showed that the adsorption efficiencies of Ir(IV), Pt(IV), Ru(III) and Rh(III) were 95.3 %, 99.8 %, 94.1 % and 43.9 %, respectively, under the following conditions: trioctylmethylammonium chloride (N263) to menthol (Men) molar ratio of 1:2, adsorbent dosage of 20 g L−1, initial aqueous phase pH of 0.1, adsorption time of 2 h, and adsorption temperature of 298.15 K. Under optimal process conditions, the maximum loading of Ir(IV), Pt(IV), Ru(III), and Rh(III) were 19.4 mg g−1, 20.6 mg g−1, 4.6 mg g−1 and 4.3 mg g−1, respectively. The adsorption process of precious metal ions obeys the Langmuir model and quasi-second-order kinetic model, which is mainly controlled by the chemical reaction of the monomolecular layer. The surface loaded HDES of XAD-2-HDES provides abundant adsorption reaction sites, and the adsorption process is mainly driven by electrostatic attraction. The complex ions of precious metals undergo an anion-exchange reaction with Cl− in N263 to form a stable hydrophobic type neutral complex species with N atoms as a bridge with HDES through ligand bonding, and form a new hydrogen-bonding network with the –OH group of Men to facilitate the dissolution of the complex.
{"title":"Study on the adsorption of precious metals from wastewater by XAD-2 resin loaded with functionalized deep eutectic solvent","authors":"Yifan Wang , Yonghui Song , Xinwei Zhang , Ping Dong , Ning Yin , Zeyu Wang , Shilei Lang","doi":"10.1016/j.hydromet.2025.106520","DOIUrl":"10.1016/j.hydromet.2025.106520","url":null,"abstract":"<div><div>This study prepared a novel adsorption material XAD-2-HDES with fast adsorption rate by impregnating XAD-2 resin with quaternary ammonium hydrophobic deep eutectic solvent (HDES). It was applied to the enrichment and recovery of various precious metal ions in aqua regia solution. The results showed that the adsorption efficiencies of Ir(IV), Pt(IV), Ru(III) and Rh(III) were 95.3 %, 99.8 %, 94.1 % and 43.9 %, respectively, under the following conditions: trioctylmethylammonium chloride (N263) to menthol (Men) molar ratio of 1:2, adsorbent dosage of 20 g L<sup>−1</sup>, initial aqueous phase pH of 0.1, adsorption time of 2 h, and adsorption temperature of 298.15 K. Under optimal process conditions, the maximum loading of Ir(IV), Pt(IV), Ru(III), and Rh(III) were 19.4 mg g<sup>−1</sup>, 20.6 mg g<sup>−1</sup>, 4.6 mg g<sup>−1</sup> and 4.3 mg g<sup>−1</sup>, respectively. The adsorption process of precious metal ions obeys the Langmuir model and quasi-second-order kinetic model, which is mainly controlled by the chemical reaction of the monomolecular layer. The surface loaded HDES of XAD-2-HDES provides abundant adsorption reaction sites, and the adsorption process is mainly driven by electrostatic attraction. The complex ions of precious metals undergo an anion-exchange reaction with Cl<sup>−</sup> in N263 to form a stable hydrophobic type neutral complex species with N atoms as a bridge with HDES through ligand bonding, and form a new hydrogen-bonding network with the –OH group of Men to facilitate the dissolution of the complex.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106520"},"PeriodicalIF":4.8,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144307831","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-06-16DOI: 10.1016/j.hydromet.2025.106522
Hari S. Jammulamadaka, Mohammad Rezaee, Sarma V. Pisupati
Red mud, the fine iron-rich residue generated during the processing of bauxite using the Bayer process, is a highly alkaline hazardous waste with significant environmental implications. While it is predominantly stored in landfills, only a small fraction is repurposed, such as in construction materials. Notably, red mud contains elevated concentrations of Scandium, a critical mineral with growing industrial demand. Over the past few decades, numerous methods have been investigated for scandium recovery from red mud. However, no commercial processes have yet been implemented at scale. This review critically examines these methods, emphasizing the influence of iron on scandium recovery. It concludes by outlining three promising scandium recovery approaches: (i) reduction roasting followed by acid baking and water leaching of the slag, (ii) acid-baking combined with ball-mill assisted water leaching, and (iii) two-stage acid-baking and water leaching.
{"title":"Unlocking scandium from red mud: A critical review of challenges, opportunities, and recovery methods","authors":"Hari S. Jammulamadaka, Mohammad Rezaee, Sarma V. Pisupati","doi":"10.1016/j.hydromet.2025.106522","DOIUrl":"10.1016/j.hydromet.2025.106522","url":null,"abstract":"<div><div>Red mud, the fine iron-rich residue generated during the processing of bauxite using the Bayer process, is a highly alkaline hazardous waste with significant environmental implications. While it is predominantly stored in landfills, only a small fraction is repurposed, such as in construction materials. Notably, red mud contains elevated concentrations of Scandium, a critical mineral with growing industrial demand. Over the past few decades, numerous methods have been investigated for scandium recovery from red mud. However, no commercial processes have yet been implemented at scale. This review critically examines these methods, emphasizing the influence of iron on scandium recovery. It concludes by outlining three promising scandium recovery approaches: (i) reduction roasting followed by acid baking and water leaching of the slag, (ii) acid-baking combined with ball-mill assisted water leaching, and (iii) two-stage acid-baking and water leaching.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106522"},"PeriodicalIF":4.8,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144535875","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The sulfuric acid roasting – water leaching - solvent extraction process is an effective method for extracting aluminum and lithium from overhaul slag. This study aims to investigate the extraction behavior of di-(2-ethylhexyl) phosphoric acid (P204) of molecular formula C16H35O4P in sulfonated kerosene for Al3+, Li+ in sulfuric acid media. Under the most suitable conditions of pH 2.7, organic and aqueous phase volume ratio (O/A) of 1, P204 concentration of 50 % (v/v), extraction time of 5 min, the selective extraction efficiency of aluminum reached 99.1 % after 3 stages. The loss of lithium was 6.2 %, with a separation factor (β(Al/Li)) of 4295. The aluminum-bearing organic phase was stripped with 20 % sulfuric acid, at an O/A phase ratio of 1. The recovery of aluminum attained 98.6 % after a stripping time of 4 min. Then, the organic phase was recycled and the inorganic phase was prepared to produce Al2(SO4)3. Finally, the high Al3+ concentration of 11.5 g/L in the acid roasting leachate of overhaul slag was reduced to 4.24 × 10−3 g/L.
{"title":"Separation of aluminum and lithium in sulfuric acid roasting leachate of overhaul slag by Di-(2-ethylhexyl) phosphoric acid extraction and sulfuric acid stripping","authors":"Liangmin Dong , Fen Jiao , Wei Liu , Zheyi Zhang , Wenqing Qin","doi":"10.1016/j.hydromet.2025.106521","DOIUrl":"10.1016/j.hydromet.2025.106521","url":null,"abstract":"<div><div>The sulfuric acid roasting – water leaching - solvent extraction process is an effective method for extracting aluminum and lithium from overhaul slag. This study aims to investigate the extraction behavior of di-(2-ethylhexyl) phosphoric acid (P204) of molecular formula C<sub>16</sub>H<sub>35</sub>O<sub>4</sub>P in sulfonated kerosene for Al<sup>3+</sup>, Li<sup>+</sup> in sulfuric acid media. Under the most suitable conditions of pH 2.7, organic and aqueous phase <em>v</em>olume ratio (O/A) of 1, P204 concentration of 50 % (<em>v</em>/v), extraction time of 5 min, the selective extraction efficiency of aluminum reached 99.1 % after 3 stages. The loss of lithium was 6.2 %, with a separation factor (β<sub>(Al/Li)</sub>) of 4295. The aluminum-bearing organic phase was stripped with 20 % sulfuric acid, at an O/A phase ratio of 1. The recovery of aluminum attained 98.6 % after a stripping time of 4 min. Then, the organic phase was recycled and the inorganic phase was prepared to produce Al<sub>2</sub>(SO<sub>4</sub>)<sub>3</sub>. Finally, the high Al<sup>3+</sup> concentration of 11.5 g/L in the acid roasting leachate of overhaul slag was reduced to 4.24 × 10<sup>−3</sup> g/L.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106521"},"PeriodicalIF":4.8,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144307832","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-06-15DOI: 10.1016/j.hydromet.2025.106517
Yanfei Fan , Dongdong Li , Ziyu Zhuang , Dandan Gao , Dewen Zeng
The caustic addition process to Li2SO4 leachate is a principal industrial process in producing lithium hydroxide. This process relies on the double-decomposition reaction between Li2SO4 and NaOH in an aqueous system, followed by cooling to separate Na2SO4∙10H2O and evaporation to produce LiOH∙H2O. Due to the presence of Na and K impurities in lithium minerals, the operation takes place in the complex aqueous system Li-Na-K-OH-SO4-H2O. This work describes: (i) the development of a thermodynamic model for the complex Li-Na-K-OH-SO4-H2O system, (ii) validation of its reliability and (iii) quantitative simulation of lithium-hydroxide production. The results led to four key conclusions: 1) A relatively low concentration (Li < 20 g/L) in the caustic solution prevents the formation of Li2SO4∙3Na2SO4∙12H2O, the principal source of lithium loss. 2) The optimal cooling temperature for removing Na2SO4∙10H2O is −10 to −15 °C. 3) A moderate evaporation temperature (50–60 °C) is critical for achieving the high recovery of LiOH∙H2O in a single cycle. 4) The mother liquor remaining after the crystallisation of LiOH∙H2O can be fully recycled. Theoretically, Na and K are completely removed as Na2SO4∙10H2O and NaK3(SO4)2 solids.
{"title":"Thermodynamic modelling of the Li-Na-K-OH-SO4-H2O system for lithium hydroxide production simulation","authors":"Yanfei Fan , Dongdong Li , Ziyu Zhuang , Dandan Gao , Dewen Zeng","doi":"10.1016/j.hydromet.2025.106517","DOIUrl":"10.1016/j.hydromet.2025.106517","url":null,"abstract":"<div><div>The caustic addition process to Li<sub>2</sub>SO<sub>4</sub> leachate is a principal industrial process in producing lithium hydroxide. This process relies on the double-decomposition reaction between Li<sub>2</sub>SO<sub>4</sub> and NaOH in an aqueous system, followed by cooling to separate Na<sub>2</sub>SO<sub>4</sub>∙10H<sub>2</sub>O and evaporation to produce LiOH∙H<sub>2</sub>O. Due to the presence of Na and K impurities in lithium minerals, the operation takes place in the complex aqueous system Li-Na-K-OH-SO<sub>4</sub>-H<sub>2</sub>O. This work describes: (i) the development of a thermodynamic model for the complex Li-Na-K-OH-SO<sub>4</sub>-H<sub>2</sub>O system, (ii) validation of its reliability and (iii) quantitative simulation of lithium-hydroxide production. The results led to four key conclusions: 1) A relatively low concentration (Li < 20 g/L) in the caustic solution prevents the formation of Li<sub>2</sub>SO<sub>4</sub>∙3Na<sub>2</sub>SO<sub>4</sub>∙12H<sub>2</sub>O, the principal source of lithium loss. 2) The optimal cooling temperature for removing Na<sub>2</sub>SO<sub>4</sub>∙10H<sub>2</sub>O is −10 to −15 °C. 3) A moderate evaporation temperature (50–60 °C) is critical for achieving the high recovery of LiOH∙H<sub>2</sub>O in a single cycle. 4) The mother liquor remaining after the crystallisation of LiOH∙H<sub>2</sub>O can be fully recycled. Theoretically, Na and K are completely removed as Na<sub>2</sub>SO<sub>4</sub>∙10H<sub>2</sub>O and NaK<sub>3</sub>(SO<sub>4</sub>)<sub>2</sub> solids.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106517"},"PeriodicalIF":4.8,"publicationDate":"2025-06-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144307828","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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