Pub Date : 2025-12-29DOI: 10.1016/j.hydromet.2025.106627
Ning Luo, Jiantao Ju, Wenke Guo, Linbo Li, Jialiang An
Secondary aluminum dross (SAD) is a hazardous waste containing fluorides and salts that pose environmental risks. An ultrasound-assisted hydrolysis process was developed to treat SAD. Compared with conventional hydrolysis, this method reduced the reaction temperature by 15 °C and time by 2 h, increased gas release by approximately 35 %, and improved leaching efficiencies of F−, Cl−, and NH4+ by 30 %, 11 %, and 14 %, respectively. Ultrasound enhanced dissolution of soluble salts (e.g., NaCl and KCl), accelerated hydrolysis of aluminum-containing phases via cavitation and microjet effects, and improved Al(OH)3 crystallinity, particle uniformity, and purity. The XPS and FT-IR analysis confirmed effective cleavage of C − H and O − H bonds and faster hydrate conversion. This energy-efficient hydrometallurgical method reduces environmental impact and enables sustainable resource recovery from SAD.
{"title":"Ultrasound-assisted hydrolysis of secondary aluminum dross and mechanism: Reducing environmental impact and improving resource recovery","authors":"Ning Luo, Jiantao Ju, Wenke Guo, Linbo Li, Jialiang An","doi":"10.1016/j.hydromet.2025.106627","DOIUrl":"10.1016/j.hydromet.2025.106627","url":null,"abstract":"<div><div>Secondary aluminum dross (SAD) is a hazardous waste containing fluorides and salts that pose environmental risks. An ultrasound-assisted hydrolysis process was developed to treat SAD. Compared with conventional hydrolysis, this method reduced the reaction temperature by 15 °C and time by 2 h, increased gas release by approximately 35 %, and improved leaching efficiencies of F<sup>−</sup>, Cl<sup>−</sup>, and NH<sub>4</sub><sup>+</sup> by 30 %, 11 %, and 14 %, respectively. Ultrasound enhanced dissolution of soluble salts (e.g., NaCl and KCl), accelerated hydrolysis of aluminum-containing phases via cavitation and microjet effects, and improved Al(OH)<sub>3</sub> crystallinity, particle uniformity, and purity. The XPS and FT-IR analysis confirmed effective cleavage of C − H and O − H bonds and faster hydrate conversion. This energy-efficient hydrometallurgical method reduces environmental impact and enables sustainable resource recovery from SAD.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"240 ","pages":"Article 106627"},"PeriodicalIF":4.8,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880006","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 : 2025-12-24DOI: 10.1016/j.hydromet.2025.106620
Xiaozhou Zhou , Tong Zhong , Wenjuan Guan , Mingyu Wang , Shengxi Wu , Xinsheng Wu , Zuoying Cao , Qinggang Li , Guiqing Zhang
Lepidolite is one of the important resources containing Li, Rb, and Cs. Currently, sulfate roasting is the predominant industrial method for processing lepidolite. However, this approach faces challenges including low comprehensive recovery, high energy consumption, and significant reagent usage. This study introduces a clean and efficient technology for recovering Li, Rb, and Cs from lepidolite, based on alkali and water cycles. The process encompasses collaborative leaching with a mixture of sodium hydroxide (NaOH) and calcium hydroxide (Ca(OH)2), selective impurity removal using Ca(OH)2, and alkaline extraction for lithium recovery. Experimental results demonstrated that the leachate could be recycled 2 times to enrich Li, Rb, and Cs. The average leaching efficiencies after 2 cycles were: 92.7 % Li, 94.3 % Rb, 94.5 % Cs, and 94.6 % K, under the leaching conditions of 400 g/L NaOH, 0.6 of mass ratio of Ca(OH)2/ore, <106 μm particle size, 5 h reaction time and 250 °C. The XRD and SEM-EDS analyses revealed that the leach residue comprised the phases Ca0.63Fe2.37Fe2(SiO4)3, NaCaHSiO4, CaF2, and Fe3O4. Furthermore, Ca(OH)₂ was employed for selective impurity removal from the solution, achieving a valuable metal loss of only 0.67 %. Subsequently, Li was efficiently recovered via synergistic solvent extraction using dodecyl phenyl methyl-β-diketone (LIX 54) and trialkylphosphine oxide (TRPO). The 85 % volume fractions of raffinate of Li could be returned to pressure leaching to reuse H2O and NaOH. The process developed in this study features environmental friendliness, high comprehensive recovery, and low reagent consumption, providing a promising approach for the clean and efficient utilization of lepidolite.
{"title":"A clean and efficient technology for lithium, rubidium, and cesium recovery from lepidolite using alkaline pressure leaching and alkaline solvent extraction with LIX 54 and TRPO","authors":"Xiaozhou Zhou , Tong Zhong , Wenjuan Guan , Mingyu Wang , Shengxi Wu , Xinsheng Wu , Zuoying Cao , Qinggang Li , Guiqing Zhang","doi":"10.1016/j.hydromet.2025.106620","DOIUrl":"10.1016/j.hydromet.2025.106620","url":null,"abstract":"<div><div>Lepidolite is one of the important resources containing Li, Rb, and Cs. Currently, sulfate roasting is the predominant industrial method for processing lepidolite. However, this approach faces challenges including low comprehensive recovery, high energy consumption, and significant reagent usage. This study introduces a clean and efficient technology for recovering Li, Rb, and Cs from lepidolite, based on alkali and water cycles. The process encompasses collaborative leaching with a mixture of sodium hydroxide (NaOH) and calcium hydroxide (Ca(OH)<sub>2</sub>), selective impurity removal using Ca(OH)<sub>2</sub>, and alkaline extraction for lithium recovery. Experimental results demonstrated that the leachate could be recycled 2 times to enrich Li, Rb, and Cs. The average leaching efficiencies after 2 cycles were: 92.7 % Li, 94.3 % Rb, 94.5 % Cs, and 94.6 % K, under the leaching conditions of 400 g/L NaOH, 0.6 of mass ratio of Ca(OH)<sub>2</sub>/ore, <106 μm particle size, 5 h reaction time and 250 °C. The XRD and SEM-EDS analyses revealed that the leach residue comprised the phases Ca<sub>0.63</sub>Fe<sub>2.37</sub>Fe<sub>2</sub>(SiO<sub>4</sub>)<sub>3</sub>, NaCaHSiO<sub>4</sub>, CaF<sub>2</sub>, and Fe<sub>3</sub>O<sub>4</sub>. Furthermore, Ca(OH)₂ was employed for selective impurity removal from the solution, achieving a valuable metal loss of only 0.67 %. Subsequently, Li was efficiently recovered via synergistic solvent extraction using dodecyl phenyl methyl-β-diketone (LIX 54) and trialkylphosphine oxide (TRPO). The 85 % volume fractions of raffinate of Li could be returned to pressure leaching to reuse H<sub>2</sub>O and NaOH. The process developed in this study features environmental friendliness, high comprehensive recovery, and low reagent consumption, providing a promising approach for the clean and efficient utilization of lepidolite.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"240 ","pages":"Article 106620"},"PeriodicalIF":4.8,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145823813","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 : 2025-12-13DOI: 10.1016/j.hydromet.2025.106626
Shuhao Dong , Yakai Yang , Hao Zhang , Meiyan Yu , Hui Guo , Ge Kuang , Haidong Wang , Xiaohui Fan
Spodumene is an important lithium-bearing mineral which naturally exists as chemically inert α phase. Therefore, a calcination process at 1100 °C is traditionally employed for phase transformation to β phase, causing a large energy consumption. This work proposes an improved alkaline autoclave method using NaOH and NaAlO2 aiming to extract lithium directly from α-spodumene. Interestingly, the addition of NaAlO2 can significantly enhance the lithium extraction efficiency from 50.5 % (dissolution with NaOH only) to 94.7 %. Moreover, the investigation of dissolution behavior indicated that the added AlO2− can capture the dissolved Si, releasing more lithium into lixivium and achieving an efficient separation of Li from Si. The lithium-containing leachate was then directly evaporated to concentrate and prepare Li2CO3. Besides, the efficiency of lithium extraction still can remain at a relatively high level around 90 % with three cyclic dissolution steps by recycled alkaline liquor. This combined autoclave method shows potential as a promising way to extract lithium directly from α-spodumene without phase transformation at high temperature.
{"title":"Enhancement of selective lithium extraction from α-spodumene by autoclaving with NaOH and NaAlO2 at 200–300 °C","authors":"Shuhao Dong , Yakai Yang , Hao Zhang , Meiyan Yu , Hui Guo , Ge Kuang , Haidong Wang , Xiaohui Fan","doi":"10.1016/j.hydromet.2025.106626","DOIUrl":"10.1016/j.hydromet.2025.106626","url":null,"abstract":"<div><div>Spodumene is an important lithium-bearing mineral which naturally exists as chemically inert α phase. Therefore, a calcination process at 1100 °C is traditionally employed for phase transformation to β phase, causing a large energy consumption. This work proposes an improved alkaline autoclave method using NaOH and NaAlO<sub>2</sub> aiming to extract lithium directly from α-spodumene. Interestingly, the addition of NaAlO<sub>2</sub> can significantly enhance the lithium extraction efficiency from 50.5 % (dissolution with NaOH only) to 94.7 %. Moreover, the investigation of dissolution behavior indicated that the added AlO<sub>2</sub><sup>−</sup> can capture the dissolved Si, releasing more lithium into lixivium and achieving an efficient separation of Li from Si. The lithium-containing leachate was then directly evaporated to concentrate and prepare Li<sub>2</sub>CO<sub>3</sub>. Besides, the efficiency of lithium extraction still can remain at a relatively high level around 90 % with three cyclic dissolution steps by recycled alkaline liquor. This combined autoclave method shows potential as a promising way to extract lithium directly from α-spodumene without phase transformation at high temperature.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"240 ","pages":"Article 106626"},"PeriodicalIF":4.8,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786600","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 : 2025-12-07DOI: 10.1016/j.hydromet.2025.106624
Thabo Sibanda, Senzo Mgabhi, Jemitias Chivavava, Alison E. Lewis
A novel method using carbon dioxide gas (CO2) and ammonia (NH3) to precipitate MnCO3 for a lithium-ion battery precursor was investigated. This MnCO3 was recovered from a high-tenor industrial MnSO4 pregnant leach solution (PLS) containing Mg2+ and Ca2+ impurities. The leach solution consisted of at least 93.9 wt% Mn2+, 2.25 wt% Mg2+, and 0.14 wt% Ca2+. In this study, results from thermodynamic simulations were compared to experimental results. The effects of pH (5.0 to 6.6) and CO2 bubbling time (1 to 12 h) were investigated in laboratory experiments where 0.4 L/min of CO2 was sparged into a 1 L agitated reactor (500 rpm) containing the PLS. The thermodynamic simulation results showed that Mn2+ recovery is optimal in the pH range of 5.9–11.7, with recovery increasing with pH. However, high Mn2+ selectivity is favourable at pH < 6.6, while moderate selectivity is achieved at pH values from 6.3 to 7.2. The experimental results showed an optimal Mn recovery of 61.3 % at a pH of 6.6 and CO2 bubbling time of 8 h. This was significantly lower than the values predicted from thermodynamic simulation (>94 % Mn recovery at pH above 5). This difference in recovery was attributed to the slow dissolution rate of CO2. The washed MnCO3 precipitate contained 99.0 wt% Mn, 0.13 wt% Ca, and 0.05 wt% Mg. This was equivalent to rejections of 97 % Mg2+ and 81 % Ca2+ from the MnCO3 precipitate, respectively. The product purity met the high-purity Mn specifications but was slightly lower than the battery-grade Mn specifications (ultra-purity Mn). This study showed that carbonate precipitation using CO2 and NH3 can selectively recover Mn2+ from an industrial MnSO4 leachate containing high Mg2+ and Ca2+ impurities, and this process has great potential for industrial application.
{"title":"A novel method using CO2 to precipitate MnCO3 for a lithium-ion battery precursor","authors":"Thabo Sibanda, Senzo Mgabhi, Jemitias Chivavava, Alison E. Lewis","doi":"10.1016/j.hydromet.2025.106624","DOIUrl":"10.1016/j.hydromet.2025.106624","url":null,"abstract":"<div><div>A novel method using carbon dioxide gas (CO<sub>2</sub>) and ammonia (NH<sub>3</sub>) to precipitate MnCO<sub>3</sub> for a lithium-ion battery precursor was investigated. This MnCO<sub>3</sub> was recovered from a high-tenor industrial MnSO<sub>4</sub> pregnant leach solution (PLS) containing Mg<sup>2+</sup> and Ca<sup>2+</sup> impurities. The leach solution consisted of at least 93.9 wt% Mn<sup>2+</sup>, 2.25 wt% Mg<sup>2+</sup>, and 0.14 wt% Ca<sup>2+</sup>. In this study, results from thermodynamic simulations were compared to experimental results. The effects of pH (5.0 to 6.6) and CO<sub>2</sub> bubbling time (1 to 12 h) were investigated in laboratory experiments where 0.4 L/min of CO<sub>2</sub> was sparged into a 1 L agitated reactor (500 rpm) containing the PLS. The thermodynamic simulation results showed that Mn<sup>2+</sup> recovery is optimal in the pH range of 5.9–11.7, with recovery increasing with pH. However, high Mn<sup>2+</sup> selectivity is favourable at pH < 6.6, while moderate selectivity is achieved at pH values from 6.3 to 7.2. The experimental results showed an optimal Mn recovery of 61.3 % at a pH of 6.6 and CO<sub>2</sub> bubbling time of 8 h. This was significantly lower than the values predicted from thermodynamic simulation (>94 % Mn recovery at pH above 5). This difference in recovery was attributed to the slow dissolution rate of CO<sub>2</sub>. The washed MnCO<sub>3</sub> precipitate contained 99.0 wt% Mn, 0.13 wt% Ca, and 0.05 wt% Mg. This was equivalent to rejections of 97 % Mg<sup>2+</sup> and 81 % Ca<sup>2+</sup> from the MnCO<sub>3</sub> precipitate, respectively. The product purity met the high-purity Mn specifications but was slightly lower than the battery-grade Mn specifications (ultra-purity Mn). This study showed that carbonate precipitation using CO<sub>2</sub> and NH<sub>3</sub> can selectively recover Mn<sup>2+</sup> from an industrial MnSO<sub>4</sub> leachate containing high Mg<sup>2+</sup> and Ca<sup>2+</sup> impurities, and this process has great potential for industrial application.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"240 ","pages":"Article 106624"},"PeriodicalIF":4.8,"publicationDate":"2025-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689597","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 : 2025-12-07DOI: 10.1016/j.hydromet.2025.106625
Cong Gao , Juhua Zhang , Xujie Hui , Wei Zhang
Brown corundum dust is a valuable gallium- containing secondary resource, with a Ga concentration ranging from 0.06 % to 0.20 %. Following alkaline leaching of brown corundum dust, a subsequent two-step carbonation-acid leaching process was implemented to reduce the levels of aluminum and silicon. However, the leachate still contained high levels of impurities, including Al, Si, K, and Fe. A solvent extraction system employing tributyl phosphate (TBP) with butyl acetate (as the diluent) was developed for the separation and purification of gallium. The mechanism by which TBP extracts gallium was elucidated by Fourier transform infrared spectroscopy, indicating an extraction reaction between the PO bond in tributyl phosphate and GaCl4−. The slope analysis determined the stoichiometric ratio of these two reactants as 0.5. The thermodynamic parameters of the extraction reaction were found as ΔHo = 40.8 kJ/mol, ΔSo = 146 J mol−1 K−1, and ΔGo = −2.58 kJ/mol. The maximum gallium loading capacity of 10 vol% TBP was determined to be 47.6 g/L. A Lewis cell was employed to investigate the influence of stirring rate, interfacial area, temperature, and reactant concentration on the kinetics of gallium extraction with TBP. The findings indicated that the extraction process was predominantly governed by the interfacial chemical reaction, exhibiting an apparent activation energy of 53.5 kJ/mol. The extraction rate equation was formulated as r0 = 0.013[Ga]1.21[TBP]0.62[HCl]0.15. In the practical solution system, the impurity elements, including Al, Si, and K, could be eliminated through solvent extraction at a rapid rate and under normal operating conditions, with the gallium extraction efficiency reaching 99.9 %.
{"title":"Thermodynamics and kinetics of gallium extraction from a leachate of brown corundum dust","authors":"Cong Gao , Juhua Zhang , Xujie Hui , Wei Zhang","doi":"10.1016/j.hydromet.2025.106625","DOIUrl":"10.1016/j.hydromet.2025.106625","url":null,"abstract":"<div><div>Brown corundum dust is a valuable gallium- containing secondary resource, with a Ga concentration ranging from 0.06 % to 0.20 %. Following alkaline leaching of brown corundum dust, a subsequent two-step carbonation-acid leaching process was implemented to reduce the levels of aluminum and silicon. However, the leachate still contained high levels of impurities, including Al, Si, K, and Fe. A solvent extraction system employing tributyl phosphate (TBP) with butyl acetate (as the diluent) was developed for the separation and purification of gallium. The mechanism by which TBP extracts gallium was elucidated by Fourier transform infrared spectroscopy, indicating an extraction reaction between the P<img>O bond in tributyl phosphate and GaCl<sub>4</sub><sup>−</sup>. The slope analysis determined the stoichiometric ratio of these two reactants as 0.5. The thermodynamic parameters of the extraction reaction were found as Δ<em>H</em><sup>o</sup> = 40.8 kJ/mol, Δ<em>S</em><sup>o</sup> = 146 J mol<sup>−1</sup> K<sup>−1</sup>, and Δ<em>G</em><sup>o</sup> = −2.58 kJ/mol. The maximum gallium loading capacity of 10 vol% TBP was determined to be 47.6 g/L. A Lewis cell was employed to investigate the influence of stirring rate, interfacial area, temperature, and reactant concentration on the kinetics of gallium extraction with TBP. The findings indicated that the extraction process was predominantly governed by the interfacial chemical reaction, exhibiting an apparent activation energy of 53.5 kJ/mol. The extraction rate equation was formulated as <em>r</em><sub>0</sub> = 0.013[Ga]<sup>1.21</sup>[TBP]<sup>0.62</sup>[HCl]<sup>0.15</sup>. In the practical solution system, the impurity elements, including Al, Si, and K, could be eliminated through solvent extraction at a rapid rate and under normal operating conditions, with the gallium extraction efficiency reaching 99.9 %.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"240 ","pages":"Article 106625"},"PeriodicalIF":4.8,"publicationDate":"2025-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689603","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 : 2025-12-02DOI: 10.1016/j.hydromet.2025.106623
José Helber Vinco, Heitor Augusto Duarte, Denise Crocce Romano Espinosa, Jorge Alberto Soares Tenório
Vanadium (V), predominantly used in steel production, is also a critical element for energy storage in redox flow batteries; however, producing high-purity vanadium remains challenging. This study reports, for the first time, the use of the anion-exchange resin LSC775(SO4) (polystyrene-based and in the sulfate form) for selective vanadium recovery from a real industrial leachate, motivated by vanadium(V) predominating as anionic vanadate species at the working pH. The feed solution originated from a secondary aqueous heap leaching, following alkaline roasting and primary leaching of vanadiferous titanomagnetite. It had a highly alkaline pH (10.3) and contained 3.7 g L−1 V (∼33 %), with major contaminants Na, Si, and K (∼67 %) and minor Ca, Mg, P, Mo, Al, and Fe (∼0.2 %). Batch adsorption experiments were carried out to evaluate vanadium uptake, including equilibrium, kinetics, and thermodynamics. Fixed-bed column tests assessed vanadium breakthrough behavior, capacity, and resin reusability. Optimal V adsorption occurred at pH 2.0, consistent with the anion-exchange mechanism. The data followed the Langmuir isotherm and the pseudo-second order kinetic model, indicating monolayer adsorption via chemisorption. Thermodynamic parameters confirmed the process is endothermic (ΔH0 > 0) and spontaneous (ΔG0 < 0). In continuous-flow conditions (2 bed volumes per hour, 10 cycles), adsorption and elution efficiencies averaged 97.4 % and 98.9 %, respectively. The maximum adsorption capacity, per the Thomas model, was 249 mg g−1. The resin maintained high performance over multiple cycles, confirming its stability and recyclability. Vanadium was recovered by precipitation and calcination, yielding V2O5 with >99.99 % purity. This work demonstrates the first successful application of LSC775(SO4) to selective vanadium recovery from a contaminant-rich secondary leachate.
{"title":"High-purity V2O5 production from titanomagnetite leachate purified by ion exchange resin","authors":"José Helber Vinco, Heitor Augusto Duarte, Denise Crocce Romano Espinosa, Jorge Alberto Soares Tenório","doi":"10.1016/j.hydromet.2025.106623","DOIUrl":"10.1016/j.hydromet.2025.106623","url":null,"abstract":"<div><div>Vanadium (V), predominantly used in steel production, is also a critical element for energy storage in redox flow batteries; however, producing high-purity vanadium remains challenging. This study reports, for the first time, the use of the anion-exchange resin LSC775(SO<sub>4</sub>) (polystyrene-based and in the sulfate form) for selective vanadium recovery from a real industrial leachate, motivated by vanadium(V) predominating as anionic vanadate species at the working pH. The feed solution originated from a secondary aqueous heap leaching, following alkaline roasting and primary leaching of vanadiferous titanomagnetite. It had a highly alkaline pH (10.3) and contained 3.7 g L<sup>−1</sup> V (∼33 %), with major contaminants Na, Si, and K (∼67 %) and minor Ca, Mg, P, Mo, Al, and Fe (∼0.2 %). Batch adsorption experiments were carried out to evaluate vanadium uptake, including equilibrium, kinetics, and thermodynamics. Fixed-bed column tests assessed vanadium breakthrough behavior, capacity, and resin reusability. Optimal V adsorption occurred at pH 2.0, consistent with the anion-exchange mechanism. The data followed the Langmuir isotherm and the pseudo-second order kinetic model, indicating monolayer adsorption via chemisorption. Thermodynamic parameters confirmed the process is endothermic (ΔH<sup>0</sup> > 0) and spontaneous (ΔG<sup>0</sup> < 0). In continuous-flow conditions (2 bed volumes per hour, 10 cycles), adsorption and elution efficiencies averaged 97.4 % and 98.9 %, respectively. The maximum adsorption capacity, per the Thomas model, was 249 mg g<sup>−1</sup>. The resin maintained high performance over multiple cycles, confirming its stability and recyclability. Vanadium was recovered by precipitation and calcination, yielding V<sub>2</sub>O<sub>5</sub> with >99.99 % purity. This work demonstrates the first successful application of LSC775(SO<sub>4</sub>) to selective vanadium recovery from a contaminant-rich secondary leachate.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"240 ","pages":"Article 106623"},"PeriodicalIF":4.8,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145657415","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 : 2025-12-01DOI: 10.1016/j.hydromet.2025.106621
Kyoung Hun Choi , Jinmyung Jang , Sevan Bedrossian , Gisele Azimi
High-purity nickel sulfate hexahydrate (NiSO₄•6H₂O) is a critical precursor for lithium-ion battery (LIB) cathode materials, particularly in the context of battery recycling and sustainable nickel supply. This study investigates the incorporation and removal behavior of key impurities, Li+, Na+, Ca2+, Mg2+, and Co2+, during the evaporative crystallization and purification of NiSO₄•6H₂O from synthetic solutions representative of LIB leachates. Crystals were subjected to sequential displacement and repulp washing, followed by impurity mapping through stepwise dissolution. Advanced characterization using ToF-SIMS, XRD, and SEM-EDS was employed to elucidate impurity localization and uptake mechanisms. Results reveal two distinct modes of impurity incorporation. Some impurity ions (Li+, Na+, and Ca2+) were predominantly surface-adsorbed and readily removed through post-crystallization washing, while Mg2+ and Co2+ were retained within the crystal lattice via isomorphous substitution with Ni2+. A minor fraction of Li+ exhibited uniform incorporation consistent with interstitial uptake. Impurity mapping confirmed solid solution behavior for Mg2+, Co2+, and residual Li+, while ToF-SIMS validated the surface association of Na+ and Li+. Post-crystallization purification improved nickel purity from below battery-grade to 99.87 %, highlighting the importance of tailored washing strategies. These findings provide mechanistic insight into impurity behavior in hydrated nickel sulfate systems and establish a framework for optimizing crystallization and purification to meet the stringent purity demands of battery-grade materials.
{"title":"Impurity incorporation and selective removal in NiSO₄•6H₂O crystals: Mechanistic insights for battery-grade purification","authors":"Kyoung Hun Choi , Jinmyung Jang , Sevan Bedrossian , Gisele Azimi","doi":"10.1016/j.hydromet.2025.106621","DOIUrl":"10.1016/j.hydromet.2025.106621","url":null,"abstract":"<div><div>High-purity nickel sulfate hexahydrate (NiSO₄•6H₂O) is a critical precursor for lithium-ion battery (LIB) cathode materials, particularly in the context of battery recycling and sustainable nickel supply. This study investigates the incorporation and removal behavior of key impurities, Li<sup>+</sup>, Na<sup>+</sup>, Ca<sup>2+</sup>, Mg<sup>2+</sup>, and Co<sup>2+</sup>, during the evaporative crystallization and purification of NiSO₄•6H₂O from synthetic solutions representative of LIB leachates. Crystals were subjected to sequential displacement and repulp washing, followed by impurity mapping through stepwise dissolution. Advanced characterization using ToF-SIMS, XRD, and SEM-EDS was employed to elucidate impurity localization and uptake mechanisms. Results reveal two distinct modes of impurity incorporation. Some impurity ions (Li<sup>+</sup>, Na<sup>+</sup>, and Ca<sup>2+</sup>) were predominantly surface-adsorbed and readily removed through post-crystallization washing, while Mg<sup>2+</sup> and Co<sup>2+</sup> were retained within the crystal lattice via isomorphous substitution with Ni<sup>2+</sup>. A minor fraction of Li<sup>+</sup> exhibited uniform incorporation consistent with interstitial uptake. Impurity mapping confirmed solid solution behavior for Mg<sup>2+</sup>, Co<sup>2+</sup>, and residual Li<sup>+</sup>, while ToF-SIMS validated the surface association of Na<sup>+</sup> and Li<sup>+</sup>. Post-crystallization purification improved nickel purity from below battery-grade to 99.87 %, highlighting the importance of tailored washing strategies. These findings provide mechanistic insight into impurity behavior in hydrated nickel sulfate systems and establish a framework for optimizing crystallization and purification to meet the stringent purity demands of battery-grade materials.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"240 ","pages":"Article 106621"},"PeriodicalIF":4.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145650911","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 : 2025-12-01DOI: 10.1016/j.hydromet.2025.106622
Situmeang Elfrida Margaretha , Wenjing Wan , Wenjuan Guan , Mingbo Fu , Yanni An , Qinggang Li
Acid type extractants are commonly used for extracting nickel and cobalt from acid leachates of nickel laterite ore. This study aims to show the potential of the commercial acid type extractant DY319 extractant for direct co-extraction of nickel and cobalt using a synthetic sulfuric solution representing a high-pressure acid leachate of nickel laterite ore. The NMR spectroscopy characterized DY319 which has a molecular formula of C16H32O2 with compound name of 4-hexyl decanoic acid. The FTIR spectroscopy of the loaded organic phase showed of the involvement of C=O group in a metal-ligand complex formation. The selectivity order of metal for DY319 followed the sequence: Cu > Zn > Ni > Co > Mn > Ca > Mg and this extractant operated better at room temperature. The McCabe-Thiele plots of the extraction at O/A phase volume ratio 1:3 with initial solution pH of 5 showed the need for 3 stages of extraction to completely separate nickel and cobalt from the solution. The stripping results indicated that nickel and cobalt can be stripped easily in low H2SO4 concentration with a stripping efficiency of 99.5 % for nickel and 92.4 % for cobalt. The multi-stage counter-current extraction of DY319 test was conducted and resulted in an extraction efficiency of 98.4 % Ni and 95.3 % Co. The use of D2EHPA removed impurities and resulted a final solution of 113 g/L Ni, 4.73 g/L Co, and impurities below 2 mg/L.
酸型萃取剂通常用于从红土镍矿酸浸出液中萃取镍和钴。本研究旨在展示商用酸型萃取剂DY319在红土镍矿高压酸浸出液合成硫酸溶液中直接共萃取镍和钴的潜力。负载有机相的FTIR光谱表明，C=O基团参与了金属配体配合物的形成。金属对DY319的选择性顺序为Cu >； Zn > Ni > Co > Mn > Ca > Mg，该萃取剂在室温下的萃取效果较好。在O/A相体积比为1:3、初始溶液pH为5的条件下，提取的McCabe-Thiele图显示，需要3个萃取阶段才能将镍和钴从溶液中完全分离出来。结果表明，在低H2SO4浓度条件下，镍和钴均可轻松剥离，镍和钴的剥离效率分别为99.5%和92.4%。对DY319进行了多级逆流萃取试验，镍和钴的提取率分别为98.4%和95.3%。采用D2EHPA对杂质进行了去除，最终溶液中镍和钴分别为113 g/L和4.73 g/L，杂质均低于2 mg/L。
{"title":"Direct co-extraction of nickel and cobalt from sulfuric acid leachate of laterite ore using extractant DY319 in kerosene followed by impurity removal using D2EHPA to produce high purity mixed concentrated solution","authors":"Situmeang Elfrida Margaretha , Wenjing Wan , Wenjuan Guan , Mingbo Fu , Yanni An , Qinggang Li","doi":"10.1016/j.hydromet.2025.106622","DOIUrl":"10.1016/j.hydromet.2025.106622","url":null,"abstract":"<div><div>Acid type extractants are commonly used for extracting nickel and cobalt from acid leachates of nickel laterite ore. This study aims to show the potential of the commercial acid type extractant DY319 extractant for direct co-extraction of nickel and cobalt using a synthetic sulfuric solution representing a high-pressure acid leachate of nickel laterite ore. The NMR spectroscopy characterized DY319 which has a molecular formula of C<sub>16</sub>H<sub>32</sub>O<sub>2</sub> with compound name of 4-hexyl decanoic acid. The FTIR spectroscopy of the loaded organic phase showed of the involvement of C=O group in a metal-ligand complex formation. The selectivity order of metal for DY319 followed the sequence: Cu > Zn > Ni > Co > Mn > Ca > Mg and this extractant operated better at room temperature. The McCabe-Thiele plots of the extraction at O/A phase volume ratio 1:3 with initial solution pH of 5 showed the need for 3 stages of extraction to completely separate nickel and cobalt from the solution. The stripping results indicated that nickel and cobalt can be stripped easily in low H<sub>2</sub>SO<sub>4</sub> concentration with a stripping efficiency of 99.5 % for nickel and 92.4 % for cobalt. The multi-stage counter-current extraction of DY319 test was conducted and resulted in an extraction efficiency of 98.4 % Ni and 95.3 % Co. The use of D2EHPA removed impurities and resulted a final solution of 113 g/L Ni, 4.73 g/L Co, and impurities below 2 mg/L.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"240 ","pages":"Article 106622"},"PeriodicalIF":4.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682026","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 : 2025-11-28DOI: 10.1016/j.hydromet.2025.106619
Joydip Mondal, Shen Long, Jie Wu
Gypsum scale formation is a major challenge in many unit operations within the minerals processing industry. Conventional techniques for removing such scales in mixing tanks are time-consuming, labour-intensive and potentially hazardous, highlighting the need for new inhibition strategies. An experimental study on the effect of ultrasound in inhibiting gypsum scale in mixing tanks at laboratory scale was conducted. A 2 L cylindrical tank, employing an unbaffled agitator system and ultrasonic transducer, was used to test the effect of varying sonication times (1 to 6 h per day), and power levels (3 to 4.25 W). Scale-mitigation parameters based on the area fraction of descaled surface, the total scale mass and scale thickness were proposed and assessed. Results revealed that intermittent application of ultrasound significantly reduces gypsum scale deposition, while the scale inhibition improved with an increase in sonication time and power. The most effective setup was found to be 6 h/day of ultrasound at 4.25 W, which achieved almost 97 % reduction in scale mass and thickness at the end of five days of scaling compared to cases without ultrasound. Acoustic analysis indicated that ultrasonic waves with multiple frequencies between 20 and 400 kHz, alongside cavitation and streaming flows, help inhibit scale formation on the tank surfaces.
{"title":"The use of ultrasound technology for the inhibition of mineral scale formation in mixing tanks","authors":"Joydip Mondal, Shen Long, Jie Wu","doi":"10.1016/j.hydromet.2025.106619","DOIUrl":"10.1016/j.hydromet.2025.106619","url":null,"abstract":"<div><div>Gypsum scale formation is a major challenge in many unit operations within the minerals processing industry. Conventional techniques for removing such scales in mixing tanks are time-consuming, labour-intensive and potentially hazardous, highlighting the need for new inhibition strategies. An experimental study on the effect of ultrasound in inhibiting gypsum scale in mixing tanks at laboratory scale was conducted. A 2 L cylindrical tank, employing an unbaffled agitator system and ultrasonic transducer, was used to test the effect of varying sonication times (1 to 6 h per day), and power levels (3 to 4.25 W). Scale-mitigation parameters based on the area fraction of descaled surface, the total scale mass and scale thickness were proposed and assessed. Results revealed that intermittent application of ultrasound significantly reduces gypsum scale deposition, while the scale inhibition improved with an increase in sonication time and power. The most effective setup was found to be 6 h/day of ultrasound at 4.25 W, which achieved almost 97 % reduction in scale mass and thickness at the end of five days of scaling compared to cases without ultrasound. Acoustic analysis indicated that ultrasonic waves with multiple frequencies between 20 and 400 kHz, alongside cavitation and streaming flows, help inhibit scale formation on the tank surfaces.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"240 ","pages":"Article 106619"},"PeriodicalIF":4.8,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682025","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 : 2025-11-22DOI: 10.1016/j.hydromet.2025.106618
Anssi Karppinen, Henna Liljanko, Sipi Seisko, Mari Lundström
Lithium-ion batteries require number of metals which have been listed as critical raw materials in European Union due to their supply risk and economic importance. Therefore, more emphasis needs to be put on (i) recycling of spent batteries, (ii) utilizing other secondary sources of battery metals and primary mining waste. In this research, leaching of battery metals from cathode materials—lithium cobalt oxide (LCO) and lithium nickel manganese cobalt oxide (NMC111)—was investigated with the aim to use waste fraction of primary mining, namely sulfide-rich flotation tailings, as reductant. Two types of tailings were investigated in the current study: pyrrhotite-pyrite tailings and pyrite tailings. These tailings contain reductive power necessary for leaching, as well as battery metals incorporated in the sulfide matrix. The investigated parameters were temperature (40–80 °C) and mass ratio of cathode material and tailings (0.5–2 g/g) whereas S/L-ratio (100 g/L), acid concentration ([H2SO4] = 1 M), and leaching time (180 min) were kept constant. The results showed that both pyrrhotite-pyrite as well as pyrite dominated tailings can act as an effective reductant for the leaching of metals from cathode materials. The extraction efficiency of battery metals correlate with dissolved iron concentration. When only pyrite tailings were used in the process, the reductive effect of S22− could also be recognized as lower concentration of dissolved Fe2+ was required when compared to use of pyrrhotite tailings. At 80 °C, LCO and NMC could be completely dissolved within 60min while simultaneous extraction of battery metals from sulfide flotation tailings was up to 17 % of Ni, 15 % of Co, and 27 % of Cu.
{"title":"Integrated acid leaching of spent battery cathode material (LCO, NMC111) and flotation tailings of pyrite and pyrrhotite","authors":"Anssi Karppinen, Henna Liljanko, Sipi Seisko, Mari Lundström","doi":"10.1016/j.hydromet.2025.106618","DOIUrl":"10.1016/j.hydromet.2025.106618","url":null,"abstract":"<div><div>Lithium-ion batteries require number of metals which have been listed as critical raw materials in European Union due to their supply risk and economic importance. Therefore, more emphasis needs to be put on (i) recycling of spent batteries, (ii) utilizing other secondary sources of battery metals and primary mining waste. In this research, leaching of battery metals from cathode materials—lithium cobalt oxide (LCO) and lithium nickel manganese cobalt oxide (NMC111)—was investigated with the aim to use waste fraction of primary mining, namely sulfide-rich flotation tailings, as reductant. Two types of tailings were investigated in the current study: pyrrhotite-pyrite tailings and pyrite tailings. These tailings contain reductive power necessary for leaching, as well as battery metals incorporated in the sulfide matrix. The investigated parameters were temperature (40–80 °C) and mass ratio of cathode material and tailings (0.5–2 g/g) whereas S/L-ratio (100 g/L), acid concentration ([H<sub>2</sub>SO<sub>4</sub>] = 1 M), and leaching time (180 min) were kept constant. The results showed that both pyrrhotite-pyrite as well as pyrite dominated tailings can act as an effective reductant for the leaching of metals from cathode materials. The extraction efficiency of battery metals correlate with dissolved iron concentration. When only pyrite tailings were used in the process, the reductive effect of S<sub>2</sub><sup>2−</sup> could also be recognized as lower concentration of dissolved Fe<sup>2+</sup> was required when compared to use of pyrrhotite tailings. At 80 °C, LCO and NMC could be completely dissolved within 60min while simultaneous extraction of battery metals from sulfide flotation tailings was up to 17 % of Ni, 15 % of Co, and 27 % of Cu.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"240 ","pages":"Article 106618"},"PeriodicalIF":4.8,"publicationDate":"2025-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145575458","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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