Pub Date : 2025-10-01Epub 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":"2025-10-01","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}
Pub Date : 2025-10-01Epub Date: 2025-07-14DOI: 10.1016/j.hydromet.2025.106535
Frank K. Crundwell
The dissolution of minerals is central to many fields of research interest, including hydrometallurgy, materials science, and geochemistry. The successful development of a comprehensive understanding of the mechanism of dissolution will have an impact on these fields. The challenge for the dissolution of gypsum is that rate of dissolution is proportional to the molar concentration of the dissolved salt, yet the solubility product is proportional to the square of the molar concentration of dissolved salt. Deriving an expression that is consistent with both the kinetics and thermodynamics has vexed researchers for decades. Furthermore, the zeta potential of gypsum shows no clear dependence on pH. In this paper, we show that the experimental data for the kinetics of dissolution, the thermodynamics describing the solubility product, and the zeta potential describing the surface charge are reconciled by accounting for the surface charge using the surface vacancy model of dissolution, and in doing so provide insight into the elementary steps involved in the dissolution of gypsum.
{"title":"On the mechanism of the dissolution of gypsum (calcium sulfate dihydrate)","authors":"Frank K. Crundwell","doi":"10.1016/j.hydromet.2025.106535","DOIUrl":"10.1016/j.hydromet.2025.106535","url":null,"abstract":"<div><div>The dissolution of minerals is central to many fields of research interest, including hydrometallurgy, materials science, and geochemistry. The successful development of a comprehensive understanding of the mechanism of dissolution will have an impact on these fields. The challenge for the dissolution of gypsum is that rate of dissolution is proportional to the molar concentration of the dissolved salt, yet the solubility product is proportional to the square of the molar concentration of dissolved salt. Deriving an expression that is consistent with both the kinetics and thermodynamics has vexed researchers for decades. Furthermore, the zeta potential of gypsum shows no clear dependence on pH. In this paper, we show that the experimental data for the kinetics of dissolution, the thermodynamics describing the solubility product, and the zeta potential describing the surface charge are reconciled by accounting for the surface charge using the surface vacancy model of dissolution, and in doing so provide insight into the elementary steps involved in the dissolution of gypsum.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106535"},"PeriodicalIF":4.8,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144656395","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 : 2025-10-01Epub 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":"2025-10-01","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 : 2025-10-01Epub Date: 2025-05-06DOI: 10.1016/j.hydromet.2025.106495
Chunxiao Zhao , Baojun Yang , Shan Hu , Jun Wang , Yang Liu , Guanzhou Qiu
Traditionally, ammonium sulfate (NH4)2SO4 has been utilised as the leaching agent in the extraction of ion-adsorption type rare earth (IATRE) ores. However, this method only extracts rare earth elements (REEs) from the ion-exchangeable phase, leaving behind a substantial amount of tailings that still contain REEs. Therefore, this study explored the bioleaching process of IATRE ores and tailings in the presence of Acidithiobacillus ferrooxidans (A. ferrooxidans) and the reaction mechanism. The results showed that in the two-step bioleaching system, where bacteria were cultured well prior to the addition of minerals for leaching, the extraction efficiencies for La (99.5 %), Ce (78.1 %), Nd (95.8 %), and Y (93.5 %) at a pyrite to IATRE ore mass ratio of 1.5:1 were 23.1 %, 58.3 %, 23.4 %, and 13.8 % higher, respectively, than those obtained using the current (NH4)2SO4 leaching system. X-ray diffraction (XRD), scanning electron microscope coupled with energy-dispersive X-ray spectroscopy (SEM-EDS), and three-dimensional excitation-emission matrix (3DEEM) revealed the bioleaching mechanisms of the IATRE ore. These results demonstrated that the oxidative dissolution of pyrite by A. ferrooxidans promoted the production of acid and Fe2+. This facilitated proton exchange reactions between H+ and IATRE ores, the acid dissolution of IATRE ores, and the reduction of Ce4+ in the colloidal sediment phase. Additionally, bacterial surface groups and extracellular polymeric substances (EPS) produced by the bacteria formed complexes with rare earth ions, facilitating the release of REEs from IATRE ores. Furthermore, A. ferrooxidans successfully extracted REEs from IATRE tailings after leaching with (NH4)2SO4. These findings provide valuable insights into the bioleaching of IATRE ores and present a novel approach for the adequate recovery of REEs from IATRE ores and tailings.
{"title":"Bioleaching and mechanism of ion-adsorption type rare earth ores and tailings using Acidithiobacillus ferrooxidans","authors":"Chunxiao Zhao , Baojun Yang , Shan Hu , Jun Wang , Yang Liu , Guanzhou Qiu","doi":"10.1016/j.hydromet.2025.106495","DOIUrl":"10.1016/j.hydromet.2025.106495","url":null,"abstract":"<div><div>Traditionally, ammonium sulfate (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub> has been utilised as the leaching agent in the extraction of ion-adsorption type rare earth (IATRE) ores. However, this method only extracts rare earth elements (REEs) from the ion-exchangeable phase, leaving behind a substantial amount of tailings that still contain REEs. Therefore, this study explored the bioleaching process of IATRE ores and tailings in the presence of <em>Acidithiobacillus ferrooxidans</em> (<em>A. ferrooxidans</em>) and the reaction mechanism. The results showed that in the two-step bioleaching system, where bacteria were cultured well prior to the addition of minerals for leaching, the extraction efficiencies for La (99.5 %), Ce (78.1 %), Nd (95.8 %), and Y (93.5 %) at a pyrite to IATRE ore mass ratio of 1.5:1 were 23.1 %, 58.3 %, 23.4 %, and 13.8 % higher, respectively, than those obtained using the current (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub> leaching system. X-ray diffraction (XRD), scanning electron microscope coupled with energy-dispersive X-ray spectroscopy (SEM-EDS), and three-dimensional excitation-emission matrix (3DEEM) revealed the bioleaching mechanisms of the IATRE ore. These results demonstrated that the oxidative dissolution of pyrite by <em>A. ferrooxidans</em> promoted the production of acid and Fe<sup>2+</sup>. This facilitated proton exchange reactions between H<sup>+</sup> and IATRE ores, the acid dissolution of IATRE ores, and the reduction of Ce<sup>4+</sup> in the colloidal sediment phase. Additionally, bacterial surface groups and extracellular polymeric substances (EPS) produced by the bacteria formed complexes with rare earth ions, facilitating the release of REEs from IATRE ores. Furthermore, <em>A. ferrooxidans</em> successfully extracted REEs from IATRE tailings after leaching with (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub>. These findings provide valuable insights into the bioleaching of IATRE ores and present a novel approach for the adequate recovery of REEs from IATRE ores and tailings.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106495"},"PeriodicalIF":4.8,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144288874","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 : 2025-10-01Epub Date: 2025-06-06DOI: 10.1016/j.hydromet.2025.106513
Qing-hua Tian, Liang-hong Duan, Zhi-peng Xu
The conventional direct-current (DC) electrorefining process is widely used for the purification of blister copper to achieve high-purity grades. However, this process typically requires extended operational cycles and exhibits limitations in removing trace impurities such as silver and tin. To address these challenges, a pulsed electro-refining method is proposed that achieves enhanced impurity removal efficiency and shorter purification time. The experimental results showed that higher impurities removal efficiency and better appearance of high-purity copper deposits could be reached in the pulse electrolysis process. The total impurities concentration of copper products could be reduced to 0.74 mg/kg after 24 h by pulse electro-refining, which could only reach 1.24 mg/kg by DC electrolysis. Moreover, the silver and tin concentrations decreased by 95 % and 85 %, respectively. In addition, the effects of several crucial conditions during the pulsed electrolysis process were investigated, including pulse current density, pulse frequency, pulse duty ratio, and pulse electrolysis duration. The results indicated that the concentrations of all impurities apart from silicon were reduced and the purity of copper deposits reached 6 N under the experimental conditions of pulse current density of 400 A/m2, pulse frequency of 500 Hz, and pulse duty ratio of 50 % after 36 h. In summarily, the pulsed electrolysis process demonstrates excellent efficacy in producing high-purity copper.
{"title":"Pulsed electrolysis: An efficient approach to enhancing purity from 4N to 6N copper","authors":"Qing-hua Tian, Liang-hong Duan, Zhi-peng Xu","doi":"10.1016/j.hydromet.2025.106513","DOIUrl":"10.1016/j.hydromet.2025.106513","url":null,"abstract":"<div><div>The conventional direct-current (DC) electrorefining process is widely used for the purification of blister copper to achieve high-purity grades. However, this process typically requires extended operational cycles and exhibits limitations in removing trace impurities such as silver and tin. To address these challenges, a pulsed electro-refining method is proposed that achieves enhanced impurity removal efficiency and shorter purification time. The experimental results showed that higher impurities removal efficiency and better appearance of high-purity copper deposits could be reached in the pulse electrolysis process. The total impurities concentration of copper products could be reduced to 0.74 mg/kg after 24 h by pulse electro-refining, which could only reach 1.24 mg/kg by DC electrolysis. Moreover, the silver and tin concentrations decreased by 95 % and 85 %, respectively. In addition, the effects of several crucial conditions during the pulsed electrolysis process were investigated, including pulse current density, pulse frequency, pulse duty ratio, and pulse electrolysis duration. The results indicated that the concentrations of all impurities apart from silicon were reduced and the purity of copper deposits reached 6 N under the experimental conditions of pulse current density of 400 A/m<sup>2</sup>, pulse frequency of 500 Hz, and pulse duty ratio of 50 % after 36 h. In summarily, the pulsed electrolysis process demonstrates excellent efficacy in producing high-purity copper.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106513"},"PeriodicalIF":4.8,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144290928","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 : 2025-10-01Epub Date: 2025-05-28DOI: 10.1016/j.hydromet.2025.106509
Charles Kim , Brian Donovan , Jeffrey P. Fitts , Raymond S. Farinato , D.R. Nagaraj , Scott Banta , Alan C. West
Over this coming decade, copper demand in the United States is projected to increase significantly because of the energy transition to carbon-free sources. Compared to traditional hydrometallurgical processes involving oxidation, reductive leaching of copper mineral concentrates has been shown to yield significant advantages. For example, reductive leaching of chalcopyrite can be performed at ambient temperatures without intensive grinding. This could achieve high yields, reduced processing costs, all while minimizing environmental impacts.
This work explores vanadium reductive leaching of other copper mineral concentrates by measuring leaching kinetics and yields. Over 90 % of the copper was successfully extracted from copper concentrates obtained from three active mines, each with different mineral compositions, after reacting in VSO4, H2SO4 solution at room temperature for 60 min. It was shown that the addition of FeSO4 enhanced the leaching yields of copper from chalcocite (Cu2S), from 55.1 % to 100 % in concentrates having moderate iron concentrations and from 62.7 % to 82.2 % in low-iron concentrates. The copper recovery in low-iron concentrates could be increased to 99 % after leaching a second time, suggesting a staged operation may be favored. Results show that similar yields may be achieved when leaching occurs in a continuous flow reactor with residence times between 10 and 20 min. For example, 85.2 % - 100 % of iron was leached from Source 2 concentrates, and 87.7 % - 95.3 % of iron was leached from Source 3 concentrates in continuous flow leaching. The processing rate using the continuous flow reactor was 87 g/L h−1, a rate competitive with existing processing methods.
{"title":"Vanadium(II) reductive upgrading of copper sulfide concentrates via Iron leaching to facilitate stagewise oxidative copper leaching at room temperature","authors":"Charles Kim , Brian Donovan , Jeffrey P. Fitts , Raymond S. Farinato , D.R. Nagaraj , Scott Banta , Alan C. West","doi":"10.1016/j.hydromet.2025.106509","DOIUrl":"10.1016/j.hydromet.2025.106509","url":null,"abstract":"<div><div>Over this coming decade, copper demand in the United States is projected to increase significantly because of the energy transition to carbon-free sources. Compared to traditional hydrometallurgical processes involving oxidation, reductive leaching of copper mineral concentrates has been shown to yield significant advantages. For example, reductive leaching of chalcopyrite can be performed at ambient temperatures without intensive grinding. This could achieve high yields, reduced processing costs, all while minimizing environmental impacts.</div><div>This work explores vanadium reductive leaching of other copper mineral concentrates by measuring leaching kinetics and yields. Over 90 % of the copper was successfully extracted from copper concentrates obtained from three active mines, each with different mineral compositions, after reacting in VSO<sub>4</sub>, H<sub>2</sub>SO<sub>4</sub> solution at room temperature for 60 min. It was shown that the addition of FeSO<sub>4</sub> enhanced the leaching yields of copper from chalcocite (Cu<sub>2</sub>S), from 55.1 % to 100 % in concentrates having moderate iron concentrations and from 62.7 % to 82.2 % in low-iron concentrates. The copper recovery in low-iron concentrates could be increased to 99 % after leaching a second time, suggesting a staged operation may be favored. Results show that similar yields may be achieved when leaching occurs in a continuous flow reactor with residence times between 10 and 20 min. For example, 85.2 % - 100 % of iron was leached from Source 2 concentrates, and 87.7 % - 95.3 % of iron was leached from Source 3 concentrates in continuous flow leaching. The processing rate using the continuous flow reactor was 87 g/L h<sup>−1</sup>, a rate competitive with existing processing methods.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106509"},"PeriodicalIF":4.8,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144196148","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 : 2025-10-01Epub 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":"2025-10-01","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 : 2025-10-01Epub Date: 2025-05-22DOI: 10.1016/j.hydromet.2025.106505
Päivi Kinnunen , Hanna Miettinen , Christian Frilund , Pekka Simell
Electric arc furnace (EAF) dust is a by-product of the stainless-steel industry that contains significant amounts of zinc and iron as well as lead and is classified as hazardous waste. Recovering metals from the EAF dust would increase the zinc supply from waste and decrease the amount of hazardous waste. Cleaning of industrial gases using EAF dust is a potential low-cost alternative to non-regenerable primary ZnO adsorbents. The challenge is to develop further treatment methods for sulfide materials to recover their metal values and manage sulfur, by comparing the leaching of EAF before and after sulfidation with H2S. This study shows the feasibility of integrating H2S removal by adsorption at elevated temperatures using EAF dust with zinc recovery from the sulfide material of EAF after sulfidation (S-EAF) using bioleaching. In this process, sulfur- and iron-oxidizing microorganisms oxidize the sulfide mineral and leach zinc into the solution. Hydrometallurgical EAF dust recycling technologies require significant quantities of acid. A part of the acid used for leaching can be produced from the sulfide material itself, significantly reducing the need for external sulfuric acid. Integrating gas cleaning with bioleaching enables the utilisation of both the metal and captured sulfur content. The integrated sulfur capture-bioleaching concept has potential for adaptation to other oxidized waste materials beyond EAF dust.
{"title":"Integration of H2S gas cleaning and bioleaching for zinc recovery from electric arc furnace dust","authors":"Päivi Kinnunen , Hanna Miettinen , Christian Frilund , Pekka Simell","doi":"10.1016/j.hydromet.2025.106505","DOIUrl":"10.1016/j.hydromet.2025.106505","url":null,"abstract":"<div><div>Electric arc furnace (EAF) dust is a by-product of the stainless-steel industry that contains significant amounts of zinc and iron as well as lead and is classified as hazardous waste. Recovering metals from the EAF dust would increase the zinc supply from waste and decrease the amount of hazardous waste. Cleaning of industrial gases using EAF dust is a potential low-cost alternative to non-regenerable primary ZnO adsorbents. The challenge is to develop further treatment methods for sulfide materials to recover their metal values and manage sulfur, by comparing the leaching of EAF before and after sulfidation with H<sub>2</sub>S. This study shows the feasibility of integrating H<sub>2</sub>S removal by adsorption at elevated temperatures using EAF dust with zinc recovery from the sulfide material of EAF after sulfidation (S-EAF) using bioleaching. In this process, sulfur- and iron-oxidizing microorganisms oxidize the sulfide mineral and leach zinc into the solution. Hydrometallurgical EAF dust recycling technologies require significant quantities of acid. A part of the acid used for leaching can be produced from the sulfide material itself, significantly reducing the need for external sulfuric acid. Integrating gas cleaning with bioleaching enables the utilisation of both the metal and captured sulfur content. The integrated sulfur capture-bioleaching concept has potential for adaptation to other oxidized waste materials beyond EAF dust.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106505"},"PeriodicalIF":4.8,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144123459","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 : 2025-10-01Epub Date: 2025-07-03DOI: 10.1016/j.hydromet.2025.106527
Zhiyuan Chen , Zihui Jiang , Qiu Hu , Jiangtao Li
Previous studies on the leaching kinetics of molybdenite were primarily based on processing data using a contraction core model with spherical mineral particles. However, molybdenite particles exhibit a thin plate and layered structure. In this study, a model of circular particles was employed to derive the kinetic equation. The apparent activation energies of the molybdenite leaching reaction, both without mechanical activation and with mechanical activation treatment, were calculated as 55.3 kJ/mol and 49.5 kJ/mol, respectively. The layered structure of molybdenite renders its mineral particles challenging to grind during the ball milling process. Nonetheless, this process enhanced the active point of the mineral to a certain extent, thereby facilitating the leaching reaction. The rate-limiting step of the leaching reaction was identified as the chemical reaction step. Specifically, the reaction order of H2SO4 and H2O2 were determined as 0.063 and 0.959, respectively. Notably, variations in the H2O2 concentration exerted a significant impact on the leaching effect, while changes in the concentration of H2SO4 exhibited a relatively smaller effect. Additionally, molybdenite exhibited strong hydrophobic properties. The addition of surfactants improved the reaction environment and enhanced the leaching effect. The expression for leaching kinetics was defined as follows:
{"title":"Leaching kinetics of molybdenite with layered structure and hydrophobic properties in the H2SO4-H2O2-H2O system at atmospheric pressure","authors":"Zhiyuan Chen , Zihui Jiang , Qiu Hu , Jiangtao Li","doi":"10.1016/j.hydromet.2025.106527","DOIUrl":"10.1016/j.hydromet.2025.106527","url":null,"abstract":"<div><div>Previous studies on the leaching kinetics of molybdenite were primarily based on processing data using a contraction core model with spherical mineral particles. However, molybdenite particles exhibit a thin plate and layered structure. In this study, a model of circular particles was employed to derive the kinetic equation. The apparent activation energies of the molybdenite leaching reaction, both without mechanical activation and with mechanical activation treatment, were calculated as 55.3 kJ/mol and 49.5 kJ/mol, respectively. The layered structure of molybdenite renders its mineral particles challenging to grind during the ball milling process. Nonetheless, this process enhanced the active point of the mineral to a certain extent, thereby facilitating the leaching reaction. The rate-limiting step of the leaching reaction was identified as the chemical reaction step. Specifically, the reaction order of H<sub>2</sub>SO<sub>4</sub> and H<sub>2</sub>O<sub>2</sub> were determined as 0.063 and 0.959, respectively. Notably, variations in the H<sub>2</sub>O<sub>2</sub> concentration exerted a significant impact on the leaching effect, while changes in the concentration of H<sub>2</sub>SO<sub>4</sub> exhibited a relatively smaller effect. Additionally, molybdenite exhibited strong hydrophobic properties. The addition of surfactants improved the reaction environment and enhanced the leaching effect. The expression for leaching kinetics was defined as follows:<span><span><span><math><mn>1</mn><mo>−</mo><msqrt><mrow><mn>1</mn><mo>−</mo><mi>α</mi></mrow></msqrt><mo>=</mo><msub><mi>k</mi><mi>r</mi></msub><mi>t</mi><mo>=</mo><mn>7.73</mn><mo>×</mo><msup><mn>10</mn><mn>3</mn></msup><msubsup><mi>r</mi><mn>0</mn><mrow><mo>−</mo><mn>1</mn></mrow></msubsup><msubsup><mi>C</mi><mrow><mi>H</mi><mn>2</mn><mi>SO</mi><mn>4</mn></mrow><mn>0.063</mn></msubsup><msubsup><mi>C</mi><mrow><mi>H</mi><mn>2</mn><mi>O</mi><mn>2</mn></mrow><mn>0.959</mn></msubsup><msup><mi>e</mi><mrow><mo>−</mo><mfrac><mn>59706</mn><mi>RT</mi></mfrac></mrow></msup><mi>t</mi></math></span></span></span></div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106527"},"PeriodicalIF":4.8,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144572672","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 : 2025-10-01Epub Date: 2025-07-04DOI: 10.1016/j.hydromet.2025.106531
Evelyn Gaxiola-Muñiz , Ricardo Aguilar-López , Sergio A. Medina-Moreno , Edgar N. Tec-Caamal
Arsenic removal from water is still a challenge to overcome, and the biologically induced formation of scorodite offers an effective approach for treating arsenic-containing effluents from the metallurgical industry. This paper presents a model-based analysis of the dynamics of the overall bioscorodite process under different bioreactor schemes. For this purpose, a modified model was experimentally validated obtaining 0.87 < R2 < 0.99 for all variables with p-values <0.001. The validated model was able to adequately predict the dynamics of each variable, which were verified by experimental observations. Subsequently, batch, fed-batch, combined batch/continuous, single-stage, and multi-stage continuous bioreactors were investigated through simulations, testing operational variables that influence the arsenic removal capacity, such as inoculum, ion concentration, dilution rate, and seeding. A comparative basis was then established to identify the bioreactor setups that enhance the arsenic immobilization as a bioscorodite. Single-stage and cascade bioreactors had high arsenic precipitation rates (up to 3.2 g L−1 d−1) and crystal sizes around ∼150 μm. Results showed that three reactors connected in series were able to precipitate 87 % arsenic with a high fed concentration (6.2 g L−1), while a higher number of serial reactors may increase conversion but affect negatively the practicality and feasibility of the system. Combined batch/continuous scheme was useful to obtain large crystal sizes, up to 225 μm. These findings underscore the effectiveness of a model-based design for bioscorodite crystallization process, providing a promising and scalable solution for arsenic removal from industrial effluents.
从水中去除砷仍然是一个需要克服的挑战，而生物诱导形成铁球石为处理冶金工业含砷废水提供了一种有效的方法。本文提出了一个基于模型的动态分析的整体生物云母过程在不同的生物反应器方案。为此，对修正模型进行了实验验证，得到0.87 <；R2 & lt;p值为<；0.001的所有变量均为0.99。验证后的模型能够充分预测各变量的动态，并通过实验观察进行了验证。随后，通过模拟研究了间歇、补料间歇、间歇/连续组合、单级和多级连续生物反应器，测试了影响砷去除能力的操作变量，如接种量、离子浓度、稀释率和播种。然后建立了一个比较基础，以确定生物反应器设置，以提高砷作为生物污泥的固定化。单级和梯级生物反应器具有较高的砷沉淀率（高达3.2 g L−1 d−1），晶体尺寸约为~ 150 μm。结果表明，3个串联反应器可在高进料浓度（6.2 g L−1）下沉淀87%的砷，较高的串联反应器数量可能会提高转化率，但不利于系统的实用性和可行性。间歇式/连续式组合方案可获得大尺寸晶体，最高可达225 μm。这些发现强调了基于模型设计的生物蛭石结晶过程的有效性，为工业废水中的砷去除提供了一种有前途的可扩展解决方案。
{"title":"Arsenic precipitation and bioscorodite crystallization from acidic metallurgical wastewater under different bioreactor schemes: In-silico performance analysis","authors":"Evelyn Gaxiola-Muñiz , Ricardo Aguilar-López , Sergio A. Medina-Moreno , Edgar N. Tec-Caamal","doi":"10.1016/j.hydromet.2025.106531","DOIUrl":"10.1016/j.hydromet.2025.106531","url":null,"abstract":"<div><div>Arsenic removal from water is still a challenge to overcome, and the biologically induced formation of scorodite offers an effective approach for treating arsenic-containing effluents from the metallurgical industry. This paper presents a model-based analysis of the dynamics of the overall bioscorodite process under different bioreactor schemes. For this purpose, a modified model was experimentally validated obtaining 0.87 < R<sup>2</sup> < 0.99 for all variables with <em>p</em>-values <0.001. The validated model was able to adequately predict the dynamics of each variable, which were verified by experimental observations. Subsequently, batch, fed-batch, combined batch/continuous, single-stage, and multi-stage continuous bioreactors were investigated through simulations, testing operational variables that influence the arsenic removal capacity, such as inoculum, ion concentration, dilution rate, and seeding. A comparative basis was then established to identify the bioreactor setups that enhance the arsenic immobilization as a bioscorodite. Single-stage and cascade bioreactors had high arsenic precipitation rates (up to 3.2 g L<sup>−1</sup> d<sup>−1</sup>) and crystal sizes around ∼150 μm. Results showed that three reactors connected in series were able to precipitate 87 % arsenic with a high fed concentration (6.2 g L<sup>−1</sup>), while a higher number of serial reactors may increase conversion but affect negatively the practicality and feasibility of the system. Combined batch/continuous scheme was useful to obtain large crystal sizes, up to 225 μm. These findings underscore the effectiveness of a model-based design for bioscorodite crystallization process, providing a promising and scalable solution for arsenic removal from industrial effluents.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106531"},"PeriodicalIF":4.8,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144571024","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号