Pub Date : 2025-12-01Epub Date: 2025-08-27DOI: 10.1016/j.hydromet.2025.106568
Shuai Rao , Dongxing Wang , Hongyang Cao , Wei Zhu , Lijuan Duan , Zhiqiang Liu , Zhiyuan Ma
Conventional H2SO4 pressure leaching of copper anode slime exhibits limited selenium extraction efficiency owing to the undesirable precipitation of elemental selenium. To address this challenge, this study developed an innovative sequential process combining hydrothermal phase transformation, atmospheric H2SO4 leaching and stepwise reduction. Thermodynamic analysis using E-pH diagrams revealed the dissolution pathways: Cu2Se underwent stepwise transformation into soluble H2SeO3 via an intermediate CuSeO3·2H2O phase, whereas tellurium species evolved from Cu2Te to Te(OH)3+ through TeO2 intermediates. Under optimal conditions, the integrated hydrothermal conversion-atmospheric leaching process achieved extraction efficiencies of 98.9 % Cu, 98.3 % Se, and 94.8 % Te. Subsequent recovery of selenium and tellurium from the resulting leachate employed stepwise reduction and purification, yielding final products with purities of 98.4 wt% Se and 99.1 wt% Te, respectively.
{"title":"Extraction of Se and Te from copper anode slime through pressure oxidation, atmospheric H2SO4 leaching and reduction with sulfur dioxide and copper powder","authors":"Shuai Rao , Dongxing Wang , Hongyang Cao , Wei Zhu , Lijuan Duan , Zhiqiang Liu , Zhiyuan Ma","doi":"10.1016/j.hydromet.2025.106568","DOIUrl":"10.1016/j.hydromet.2025.106568","url":null,"abstract":"<div><div>Conventional H<sub>2</sub>SO<sub>4</sub> pressure leaching of copper anode slime exhibits limited selenium extraction efficiency owing to the undesirable precipitation of elemental selenium. To address this challenge, this study developed an innovative sequential process combining hydrothermal phase transformation, atmospheric H<sub>2</sub>SO<sub>4</sub> leaching and stepwise reduction. Thermodynamic analysis using E-pH diagrams revealed the dissolution pathways: Cu<sub>2</sub>Se underwent stepwise transformation into soluble H<sub>2</sub>SeO<sub>3</sub> via an intermediate CuSeO<sub>3</sub>·2H<sub>2</sub>O phase, whereas tellurium species evolved from Cu<sub>2</sub>Te to Te(OH)<sub>3</sub><sup>+</sup> through TeO<sub>2</sub> intermediates. Under optimal conditions, the integrated hydrothermal conversion-atmospheric leaching process achieved extraction efficiencies of 98.9 % Cu, 98.3 % Se, and 94.8 % Te. Subsequent recovery of selenium and tellurium from the resulting leachate employed stepwise reduction and purification, yielding final products with purities of 98.4 wt% Se and 99.1 wt% Te, respectively.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"238 ","pages":"Article 106568"},"PeriodicalIF":4.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144988979","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 : 2025-12-01Epub Date: 2025-08-28DOI: 10.1016/j.hydromet.2025.106569
Thomas Barral , Laurent Claparede , Nicolas Dacheux
The aim of this work is to study the dissolution kinetics of a series of powdered UO2+x samples with different structural and microstructural properties. For this purpose, UO2+x powders were prepared by hydroxide precipitation and then heat-treated at different temperatures under argon and reducing atmospheres. The calcined UO2+x samples were first investigated ex-situ by several physicochemical techniques in order to highlight the dependence of the normalized dissolution rates on various parameters. The PXRD experiments showed the preservation of the fluorite structure under reducing atmosphere over the whole temperature range studied, while the formation of a U3O8 phase was highlighted under argon at T ≤ 1100 °C. The study of the dissolution of UO2+x samples first highlighted the effect of increasing the calcination temperature (decrease of SSA), which significantly improves the chemical durability of the solids. The higher the calcination temperature, the lower the reactivity of the sample and the longer the time required to reach full dissolution. Secondly, the presence of a U3O8 fraction in some samples calcined under argon resulted in a higher normalized dissolution rate. For comparison, the normalized dissolution rate of a pure U3O8 sample reached RL = (5.6 ± 1.1) × 10−1 g m−2 d−1, a higher value than that of UO2+x, RL = 5.5 × 10−2 g m−2 d−1 on average. Furthermore, these samples showed no change in kinetic regime during dissolution, which could be explained by the blocking by U3O8 of the transition to a kinetic dissolution regime autocatalyzed by nitrogen species.
本研究的目的是研究一系列具有不同结构和微观结构性质的UO2+x粉末样品的溶解动力学。为此,采用氢氧化物沉淀法制备了UO2+x粉末,并在氩气和还原气氛下进行了不同温度的热处理。为了突出标准化溶解速率对各种参数的依赖性,我们首先通过几种物理化学技术对煅烧的UO2+x样品进行了非原位研究。PXRD实验表明,在整个研究温度范围内,还原性气氛下,萤石结构得以保存,而在T≤1100℃的氩气条件下,U3O8相的形成较为突出。UO2+x样品的溶解研究首先突出了提高煅烧温度(降低SSA)的效果,显著提高了固体的化学耐久性。煅烧温度越高,样品的反应性越低,达到完全溶解所需的时间越长。其次,在氩气下煅烧的一些样品中存在U3O8馏分,导致了更高的归一化溶解速率。相比之下,U3O8纯样品的标准化溶解速率RL =(5.6±1.1)× 10−1 g m−2 d−1,高于UO2+x的平均RL = 5.5 × 10−2 g m−2 d−1。此外,这些样品在溶解过程中没有表现出动力学模式的变化,这可以解释为U3O8阻断了向氮自催化的动力学溶解模式的转变。
{"title":"Impact of firing temperature and atmosphere on the chemical reactivity of UO2+x powders in nitric acid","authors":"Thomas Barral , Laurent Claparede , Nicolas Dacheux","doi":"10.1016/j.hydromet.2025.106569","DOIUrl":"10.1016/j.hydromet.2025.106569","url":null,"abstract":"<div><div>The aim of this work is to study the dissolution kinetics of a series of powdered UO<sub>2+x</sub> samples with different structural and microstructural properties. For this purpose, UO<sub>2+x</sub> powders were prepared by hydroxide precipitation and then heat-treated at different temperatures under argon and reducing atmospheres. The calcined UO<sub>2+x</sub> samples were first investigated <em>ex-situ</em> by several physicochemical techniques in order to highlight the dependence of the normalized dissolution rates on various parameters. The PXRD experiments showed the preservation of the fluorite structure under reducing atmosphere over the whole temperature range studied, while the formation of a U<sub>3</sub>O<sub>8</sub> phase was highlighted under argon at <em>T</em> ≤ 1100 °C. The study of the dissolution of UO<sub>2+x</sub> samples first highlighted the effect of increasing the calcination temperature (decrease of S<sub>SA</sub>), which significantly improves the chemical durability of the solids. The higher the calcination temperature, the lower the reactivity of the sample and the longer the time required to reach full dissolution. Secondly, the presence of a U<sub>3</sub>O<sub>8</sub> fraction in some samples calcined under argon resulted in a higher normalized dissolution rate. For comparison, the normalized dissolution rate of a pure U<sub>3</sub>O<sub>8</sub> sample reached <em>R</em><sub><em>L</em></sub> = (5.6 ± 1.1) × 10<sup>−1</sup> g m<sup>−2</sup> d<sup>−1</sup>, a higher value than that of UO<sub>2+x</sub>, <em>R</em><sub><em>L</em></sub> = 5.5 × 10<sup>−2</sup> g m<sup>−2</sup> d<sup>−1</sup> on average. Furthermore, these samples showed no change in kinetic regime during dissolution, which could be explained by the blocking by U<sub>3</sub>O<sub>8</sub> of the transition to a kinetic dissolution regime autocatalyzed by nitrogen species.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"238 ","pages":"Article 106569"},"PeriodicalIF":4.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144925967","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 : 2025-12-01Epub Date: 2025-09-29DOI: 10.1016/j.hydromet.2025.106577
Faxin Xiao , Xinyu Cao , Qingwen Ma , Cuixia Yang , Yaru Zhao , Ziqi He , Xuwei Luo , Junqiang Chen , Shuchen Sun , Ganfeng Tu
The selective removal of arsenic from zinc smelting dust is a notable measure toward resource recovery and environmental protection. In this study, a thiourea-assisted alkaline leaching method was employed to selectively extract arsenic from Zn smelting dust. The thermodynamics of arsenic dissolution were investigated first. The effects of NaOH concentration, thiourea concentration, leaching temperature, leaching time, and liquid–solid ratio on arsenic and zinc extraction during alkaline leaching were investigated. The results demonstrated that the addition of thiourea effectively enhanced arsenic extraction from 58.1 % to 77.1 %, while suppressing Zn leaching from 18.4 % to 2.6 %. Under optimal conditions, As, Zn, Fe, Pb, In, and Ag exhibited leaching efficiencies of 77.1 %, 2.6 %, 4.5 %, 2.1 %, 1.3 %, and 3.2 %, respectively, confirming selective arsenic leaching over other elements. Combined XRD, SEM, and XPS characterizations revealed that thiourea facilitated the dissolution of insoluble arsenate minerals and promoted the formation of ZnS and PbS precipitates by releasing S2− into the solution. This process effectively reduced the loss of valuable metals such as Zn and Pb. This method can be used to selectively remove arsenic from As-containing oxidized dust.
{"title":"Selective leaching of arsenic from zinc oxide dust in NaOH-(NH2)2CS solution","authors":"Faxin Xiao , Xinyu Cao , Qingwen Ma , Cuixia Yang , Yaru Zhao , Ziqi He , Xuwei Luo , Junqiang Chen , Shuchen Sun , Ganfeng Tu","doi":"10.1016/j.hydromet.2025.106577","DOIUrl":"10.1016/j.hydromet.2025.106577","url":null,"abstract":"<div><div>The selective removal of arsenic from zinc smelting dust is a notable measure toward resource recovery and environmental protection. In this study, a thiourea-assisted alkaline leaching method was employed to selectively extract arsenic from Zn smelting dust. The thermodynamics of arsenic dissolution were investigated first. The effects of NaOH concentration, thiourea concentration, leaching temperature, leaching time, and liquid–solid ratio on arsenic and zinc extraction during alkaline leaching were investigated. The results demonstrated that the addition of thiourea effectively enhanced arsenic extraction from 58.1 % to 77.1 %, while suppressing Zn leaching from 18.4 % to 2.6 %. Under optimal conditions, As, Zn, Fe, Pb, In, and Ag exhibited leaching efficiencies of 77.1 %, 2.6 %, 4.5 %, 2.1 %, 1.3 %, and 3.2 %, respectively, confirming selective arsenic leaching over other elements. Combined XRD, SEM, and XPS characterizations revealed that thiourea facilitated the dissolution of insoluble arsenate minerals and promoted the formation of ZnS and PbS precipitates by releasing S<sup>2−</sup> into the solution. This process effectively reduced the loss of valuable metals such as Zn and Pb. This method can be used to selectively remove arsenic from As-containing oxidized dust.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"238 ","pages":"Article 106577"},"PeriodicalIF":4.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145216470","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 : 2025-12-01Epub Date: 2025-08-20DOI: 10.1016/j.hydromet.2025.106554
Nazanin Bahaloo-Horeh, Farzaneh Sadri
Siderophores are low-molecular-weight, metal-chelating biometabolites that exhibit the ability to bind iron and other metal ions with high selectivity. Over 500 structurally distinct siderophores have been identified, offering diverse coordination mechanisms for potential metal complexation. Recent research has investigated their use in extracting metals from both primary and secondary sources, including ores, mine tailings, electronic waste, and industrial effluents—primarily under laboratory conditions. This review critically examines reported findings across various metal–siderophore systems, evaluating factors such as leaching parameters, synergistic use with co-lixiviants, and integration into hybrid approaches. However, no commercial applications currently exist, and significant economic and technical barriers—particularly high production costs and scalability challenges—limit practical viability. This review aims to consolidate current scientific understanding, highlight existing limitations, and outline realistic future research directions focused on overcoming technical and economic constraints to broader implementation.
{"title":"Advancements in siderophore-based technologies for metal biorecovery","authors":"Nazanin Bahaloo-Horeh, Farzaneh Sadri","doi":"10.1016/j.hydromet.2025.106554","DOIUrl":"10.1016/j.hydromet.2025.106554","url":null,"abstract":"<div><div>Siderophores are low-molecular-weight, metal-chelating biometabolites that exhibit the ability to bind iron and other metal ions with high selectivity. Over 500 structurally distinct siderophores have been identified, offering diverse coordination mechanisms for potential metal complexation. Recent research has investigated their use in extracting metals from both primary and secondary sources, including ores, mine tailings, electronic waste, and industrial effluents—primarily under laboratory conditions. This review critically examines reported findings across various metal–siderophore systems, evaluating factors such as leaching parameters, synergistic use with co-lixiviants, and integration into hybrid approaches. However, no commercial applications currently exist, and significant economic and technical barriers—particularly high production costs and scalability challenges—limit practical viability. This review aims to consolidate current scientific understanding, highlight existing limitations, and outline realistic future research directions focused on overcoming technical and economic constraints to broader implementation.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"238 ","pages":"Article 106554"},"PeriodicalIF":4.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144904031","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 : 2025-12-01Epub Date: 2025-08-30DOI: 10.1016/j.hydromet.2025.106570
Mark G. Aylmore, Martin A. Wells, Zakaria Quadir, William D.A. Rickard, Kai Rankenburg, Brent I.A. McInnes
<div><div>A suite of spodumene samples from albite-spodumene type pegmatites, mined for their lithium content, in the Archaean North Pilbara and Yilgarn Cratons regions of Western Australia, were examined to assess the influence of trace element impurities in spodumene and associated gangue phases on the thermal transformation of spodumene. Calcination of spodumene is required to convert the natural, monoclinic α-spodumene form into the tetragonal β-spodumene form, which is more amenable to recovering lithium during hydrometallurgy processing.</div><div>Spodumene contains minor concentrations of Fe (500–10,000 mg/kg), Mn (200–1400 mg/kg) and other trace element impurities incorporated within the crystal structure. Primary gangue mineralogy comprises quartz, Na/K-feldspar and mica, with secondary alteration predominantly as ‘sericitic’ phyllosilicates (muscovite-lepidolite, chlorite/cookeite mixtures) variably enriched in Fe, Mn, Mg and K relative to spodumene.</div><div>Primary and secondary mica undergo thermal dehydroxylation at temperatures (<950 °C) below the spodumene transformation temperature (970–1100 °C). Decomposed micas form melts that coat the surface and partially encapsulate the calcined spodumene grain surfaces. Feldspar decomposition at 1060 to 1200 °C, coincides with spodumene transformation, and can also result in melt formation, depending upon the composition of the feldspars (K-feldspar, albite). The thermal degradation of other mineral contaminants, such as biotite, pyroxene and amphibole from the presence of country rock (mafic, ultramafic) in the concentrate also coincides with the α- to β-spodumene phase transformation. The generated melts that coat grains can reduce the rate of α-β spodumene conversion and the subsequent ability to extract lithium from calcined spodumene.</div><div>Primary Fe and Mn impurities in spodumene, and those hosted by mica impurities within spodumene have a marked effect in decreasing the temperature of the α-γ-β spodumene conversion. Spodumene is not a strong conductor of heat, and the highly exothermic reaction of Fe and Mn oxidation within both mica and spodumene during thermal alteration affects thermal conductivity, leading to increased heat transfer within spodumene particles, which promotes the thermal transformation of spodumene at a lower temperature.</div><div>However, calcined spodumene particles with high Fe and Mn contents (> ∼ 0.5 wt%) showed black, open sintered regions, accompanied by the generation of fine (<5 μm) particles, and exsolution of Fe/Mn-oxides particles. The sintering and the generation of fines in the calciner will lead to reduced lithium recovery from calcined products.</div><div>This study illustrates the importance of minimising micaceous and feldspar components in the concentrate during the beneficiation stage, which can potentially lead to a decrease in lithium recovery during the extraction process. However, the fine-integrated nature of micas associat
{"title":"The effect and implication of impurities on the calcination of α spodumene for lithium extraction","authors":"Mark G. Aylmore, Martin A. Wells, Zakaria Quadir, William D.A. Rickard, Kai Rankenburg, Brent I.A. McInnes","doi":"10.1016/j.hydromet.2025.106570","DOIUrl":"10.1016/j.hydromet.2025.106570","url":null,"abstract":"<div><div>A suite of spodumene samples from albite-spodumene type pegmatites, mined for their lithium content, in the Archaean North Pilbara and Yilgarn Cratons regions of Western Australia, were examined to assess the influence of trace element impurities in spodumene and associated gangue phases on the thermal transformation of spodumene. Calcination of spodumene is required to convert the natural, monoclinic α-spodumene form into the tetragonal β-spodumene form, which is more amenable to recovering lithium during hydrometallurgy processing.</div><div>Spodumene contains minor concentrations of Fe (500–10,000 mg/kg), Mn (200–1400 mg/kg) and other trace element impurities incorporated within the crystal structure. Primary gangue mineralogy comprises quartz, Na/K-feldspar and mica, with secondary alteration predominantly as ‘sericitic’ phyllosilicates (muscovite-lepidolite, chlorite/cookeite mixtures) variably enriched in Fe, Mn, Mg and K relative to spodumene.</div><div>Primary and secondary mica undergo thermal dehydroxylation at temperatures (<950 °C) below the spodumene transformation temperature (970–1100 °C). Decomposed micas form melts that coat the surface and partially encapsulate the calcined spodumene grain surfaces. Feldspar decomposition at 1060 to 1200 °C, coincides with spodumene transformation, and can also result in melt formation, depending upon the composition of the feldspars (K-feldspar, albite). The thermal degradation of other mineral contaminants, such as biotite, pyroxene and amphibole from the presence of country rock (mafic, ultramafic) in the concentrate also coincides with the α- to β-spodumene phase transformation. The generated melts that coat grains can reduce the rate of α-β spodumene conversion and the subsequent ability to extract lithium from calcined spodumene.</div><div>Primary Fe and Mn impurities in spodumene, and those hosted by mica impurities within spodumene have a marked effect in decreasing the temperature of the α-γ-β spodumene conversion. Spodumene is not a strong conductor of heat, and the highly exothermic reaction of Fe and Mn oxidation within both mica and spodumene during thermal alteration affects thermal conductivity, leading to increased heat transfer within spodumene particles, which promotes the thermal transformation of spodumene at a lower temperature.</div><div>However, calcined spodumene particles with high Fe and Mn contents (> ∼ 0.5 wt%) showed black, open sintered regions, accompanied by the generation of fine (<5 μm) particles, and exsolution of Fe/Mn-oxides particles. The sintering and the generation of fines in the calciner will lead to reduced lithium recovery from calcined products.</div><div>This study illustrates the importance of minimising micaceous and feldspar components in the concentrate during the beneficiation stage, which can potentially lead to a decrease in lithium recovery during the extraction process. However, the fine-integrated nature of micas associat","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"238 ","pages":"Article 106570"},"PeriodicalIF":4.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144988978","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 : 2025-12-01Epub Date: 2025-08-22DOI: 10.1016/j.hydromet.2025.106555
Ueslei G. Favero , Ygor R. Guimarães , Nayara T.P. Martins , Nathan P. Viana , Guilherme M.D. Ferreira , Renê C. Silva , Tiago A. Silva , Maria C. Hespanhol
The pyrometallurgical process for extracting copper from chalcopyrite has disadvantages related to energy consumption and pollution due to toxic gas emissions, necessitating the adoption of more sustainable approaches for copper extraction. This study proposes a circular methodology for hydrometallurgy-based leaching of chalcopyrite concentrate, using deep eutectic solvents (DES) composed of methanesulfonic acid and choline salts as green leaching agents, focusing on waste minimization. Evaluation of leaching efficiency was performed varying the anion in the choline salt (chloride, bitartrate, or dihydrogen citrate), the solid/liquid ratio (RS-L of 0.04 and 0.02 g g−1), and the DES water content (0, 10, and 30 %). After in situ copper electrodeposition directly from the leachate obtained from chalcopyrite leaching, the residue remaining was combined with an agro-industrial biomass waste to prepare a high-performance adsorbent for removing 2,4-dichlorophenoxyacetic acid (2,4-D) from aqueous media. The DES formed with choline chloride, methanesulfonic acid, and 30 % water, used at RS-L of 0.04 g g−1, enabled the leaching of 75 % of the copper from chalcopyrite. The redox behavior of the dissolved copper in the DES leachate was investigated by cyclic voltammetry, and copper was recovered by electrodeposition as metallic copper with purity of 99 %. The adsorbent exhibited a superior 2,4-D removal capacity of 170 mg g−1, compared to other materials reported in the literature. The proposed process is a proof-of-concept that the use of DES can reduce the number of steps required for recovery of high-purity copper from chalcopyrite. This is a sustainable method that integrates material and energy flows, safely disposes of potentially harmful elements, and achieves zero-waste mining by applying combined circular hydrometallurgy principles.
从黄铜矿中提取铜的火法冶金工艺存在能源消耗和有毒气体排放造成的污染等缺点,需要采用更可持续的方法提取铜。本研究提出了一种基于湿法冶金的黄铜矿精矿浸出循环方法,使用由甲磺酸和胆碱盐组成的深共晶溶剂(DES)作为绿色浸出剂,重点是尽量减少废物。通过改变胆碱盐(氯化物、酒石酸盐或柠檬酸二氢盐)中的阴离子、固液比(RS-L分别为0.04和0.02 g g - 1)以及DES含水量(0、10和30%)来评估浸出效率。将黄铜矿浸出的渗滤液就地电沉积铜后,将其残渣与农工生物质废弃物结合,制备了一种高性能吸附剂,用于去除水中介质中的2,4-二氯苯氧乙酸(2,4- d)。以氯化胆碱、甲磺酸和30%的水为原料,在0.04 g g−1的RS-L条件下形成DES,可以从黄铜矿中浸出75%的铜。采用循环伏安法研究了DES渗滤液中溶解铜的氧化还原行为,并采用电沉积法回收了纯度为99%的金属铜。与文献中报道的其他材料相比,该吸附剂具有170 mg g−1的优越2,4- d去除能力。所提出的工艺是一个概念证明,使用DES可以减少从黄铜矿中回收高纯度铜所需的步骤数。这是一种可持续的方法,它整合了材料和能量流,安全处理潜在的有害元素,并通过应用联合循环湿法冶金原理实现零废物开采。
{"title":"Sustainable copper recovery from chalcopyrite: Eutectic solvent as a green medium for leaching, in situ electrodeposition, and platform for adsorbent modification: Preliminary attempt for a zero-waste process","authors":"Ueslei G. Favero , Ygor R. Guimarães , Nayara T.P. Martins , Nathan P. Viana , Guilherme M.D. Ferreira , Renê C. Silva , Tiago A. Silva , Maria C. Hespanhol","doi":"10.1016/j.hydromet.2025.106555","DOIUrl":"10.1016/j.hydromet.2025.106555","url":null,"abstract":"<div><div>The pyrometallurgical process for extracting copper from chalcopyrite has disadvantages related to energy consumption and pollution due to toxic gas emissions, necessitating the adoption of more sustainable approaches for copper extraction. This study proposes a circular methodology for hydrometallurgy-based leaching of chalcopyrite concentrate, using deep eutectic solvents (DES) composed of methanesulfonic acid and choline salts as green leaching agents, focusing on waste minimization. Evaluation of leaching efficiency was performed varying the anion in the choline salt (chloride, bitartrate, or dihydrogen citrate), the solid/liquid ratio (R<sub>S-L</sub> of 0.04 and 0.02 g g<sup>−1</sup>), and the DES water content (0, 10, and 30 %). After in situ copper electrodeposition directly from the leachate obtained from chalcopyrite leaching, the residue remaining was combined with an agro-industrial biomass waste to prepare a high-performance adsorbent for removing 2,4-dichlorophenoxyacetic acid (2,4-D) from aqueous media. The DES formed with choline chloride, methanesulfonic acid, and 30 % water, used at R<sub>S-L</sub> of 0.04 g g<sup>−1</sup>, enabled the leaching of 75 % of the copper from chalcopyrite. The redox behavior of the dissolved copper in the DES leachate was investigated by cyclic voltammetry, and copper was recovered by electrodeposition as metallic copper with purity of 99 %. The adsorbent exhibited a superior 2,4-D removal capacity of 170 mg g<sup>−1</sup>, compared to other materials reported in the literature. The proposed process is a proof-of-concept that the use of DES can reduce the number of steps required for recovery of high-purity copper from chalcopyrite. This is a sustainable method that integrates material and energy flows, safely disposes of potentially harmful elements, and achieves zero-waste mining by applying combined circular hydrometallurgy principles.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"238 ","pages":"Article 106555"},"PeriodicalIF":4.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144903885","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 : 2025-11-01Epub Date: 2025-07-24DOI: 10.1016/j.hydromet.2025.106548
E. Díaz-Gutiérrez , J. Hernández-Saz , José A. Maldonado Calvo , J.M. Gallardo , A. Paúl
The recovery of antimony from side stream is challenging due to impurities like arsenic and bismuth which affect extraction efficiency and product quality. This study examines the individual and combined effects of As and Bi on antimony hydrolysis from eluates produced during copper electrorefining. Synthetic and process eluates were analysed to optimise operating conditions and understand impurity interactions. Hydrolysis experiments across pH values (0.25–0.9) revealed an optimal pH range (0.6–0.7) for maximizing antimony recovery (>90 %) in impurity-free conditions. Arsenic reduced the antimony recovery by 8 %–13 %, destabilising precipitates and forming amorphous phases. Bismuth caused a smaller reduction (3 %–7 %) but had a diminished effect in the presence of As, which dominated the system's chemistry. Process eluates exhibited greater variability, particularly in extraction yields, underscoring the need to validate findings based on synthetic solutions against industrial matrices. This study provides insights into optimizing antimony recovery through impurity management and highlights the value of combining the analyses of synthetic and process eluates.
{"title":"Role of arsenic(V) and bismuth in the recovery of antimony by hydrolysis and precipitation from eluates produced during copper electrorefining","authors":"E. Díaz-Gutiérrez , J. Hernández-Saz , José A. Maldonado Calvo , J.M. Gallardo , A. Paúl","doi":"10.1016/j.hydromet.2025.106548","DOIUrl":"10.1016/j.hydromet.2025.106548","url":null,"abstract":"<div><div>The recovery of antimony from side stream is challenging due to impurities like arsenic and bismuth which affect extraction efficiency and product quality. This study examines the individual and combined effects of As and Bi on antimony hydrolysis from eluates produced during copper electrorefining. Synthetic and process eluates were analysed to optimise operating conditions and understand impurity interactions. Hydrolysis experiments across pH values (0.25–0.9) revealed an optimal pH range (0.6–0.7) for maximizing antimony recovery (>90 %) in impurity-free conditions. Arsenic reduced the antimony recovery by 8 %–13 %, destabilising precipitates and forming amorphous phases. Bismuth caused a smaller reduction (3 %–7 %) but had a diminished effect in the presence of As, which dominated the system's chemistry. Process eluates exhibited greater variability, particularly in extraction yields, underscoring the need to validate findings based on synthetic solutions against industrial matrices. This study provides insights into optimizing antimony recovery through impurity management and highlights the value of combining the analyses of synthetic and process eluates.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"237 ","pages":"Article 106548"},"PeriodicalIF":4.8,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724946","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 : 2025-11-01Epub Date: 2025-08-13DOI: 10.1016/j.hydromet.2025.106551
Huiying Shi , Yi Luo , Ying Deng , Jianhao Dai , Jianfei Zhang , Leming Ou
The recycling of spent lithium-ion batteries (LIBs) represents the terminal phase of the new energy industry chain and plays a pivotal role in resource conservation and environmental protection. Despite increasing attention, the development of green and efficient recycling strategies remains a substantial challenge. In recent years, various environmentally benign solvents—including supercritical fluids, deep eutectic solvents (DES), and ionic liquids (ILs)—have been explored to promote the sustainable recycling of LIBs. Among these, the application of biomass-derived reagents (BDRs) has emerged as a promising approach due to their renewability and low environmental impact. In this study, a novel leaching strategy employing the natural organic molecule dimethyl-β-propionic acid thiophene (DMPT) is proposed for the efficient and environmentally friendly recovery of valuable metals from spent ternary LIB cathodes. Leveraging the synergistic action of carboxyl functional groups and chloride ions inherent in the DMPT structure, leaching efficiencies of Li, Ni, Co, and Mn reached 98.7 %, 97.2 %, 97.8 %, and 98.3 %, respectively. The leaching reactions and products were systematically investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Compared with conventional hydrometallurgical processes, this DMPT-based method eliminates the need for strong acids, bases, or additional reducing agents, thus minimizing secondary pollution. The proposed approach offers a green, sustainable, and effective alternative for the recovery of critical metals from spent LIBs, and holds significant potential for future industrial application.
{"title":"Recovery of valuable metals from spent lithium-ion batteries based on a green and efficient leaching system of dimethyl-β-propionic acid thiophene (DMPT)","authors":"Huiying Shi , Yi Luo , Ying Deng , Jianhao Dai , Jianfei Zhang , Leming Ou","doi":"10.1016/j.hydromet.2025.106551","DOIUrl":"10.1016/j.hydromet.2025.106551","url":null,"abstract":"<div><div>The recycling of spent lithium-ion batteries (LIBs) represents the terminal phase of the new energy industry chain and plays a pivotal role in resource conservation and environmental protection. Despite increasing attention, the development of green and efficient recycling strategies remains a substantial challenge. In recent years, various environmentally benign solvents—including supercritical fluids, deep eutectic solvents (DES), and ionic liquids (ILs)—have been explored to promote the sustainable recycling of LIBs. Among these, the application of biomass-derived reagents (BDRs) has emerged as a promising approach due to their renewability and low environmental impact. In this study, a novel leaching strategy employing the natural organic molecule dimethyl-β-propionic acid thiophene (DMPT) is proposed for the efficient and environmentally friendly recovery of valuable metals from spent ternary LIB cathodes. Leveraging the synergistic action of carboxyl functional groups and chloride ions inherent in the DMPT structure, leaching efficiencies of Li, Ni, Co, and Mn reached 98.7 %, 97.2 %, 97.8 %, and 98.3 %, respectively. The leaching reactions and products were systematically investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Compared with conventional hydrometallurgical processes, this DMPT-based method eliminates the need for strong acids, bases, or additional reducing agents, thus minimizing secondary pollution. The proposed approach offers a green, sustainable, and effective alternative for the recovery of critical metals from spent LIBs, and holds significant potential for future industrial application.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"237 ","pages":"Article 106551"},"PeriodicalIF":4.8,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144828658","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 : 2025-11-01Epub Date: 2025-08-19DOI: 10.1016/j.hydromet.2025.106553
Jiayu Mi , Xingyu Chen , Ailiang Chen , Xuheng Liu , Jiangtao Li , Lihua He , Fenglong Sun , Zhongwei Zhao
The ammonia leaching-purification-crystallization process is the conventional treatment method of molybdenum calcine. This process generates large amounts of nitrogen-containing wastewater and exhaust gases. Based on the self-coordination principle of Mo, where MoO3 with low-polymerization ability combines with Na2MoO4 into highly polymerized polymolybdates, this study proposes a novel, green leaching process using Na2MoO4 for the selective extraction of Mo from molybdenum calcine. Leaching conditions were optimized, and the reaction mechanism was elucidated through the identification of solids using XRD, EDS mapping, XPS, and Raman spectroscopy. Results show that under optimal conditions, the leaching efficiency reached 98.6 %. Molybdenum from MoO3, PbMoO4, and FeMoO4 phases in the calcine was effectively extracted, while Fe and Pb oxides remained in the leach residue as PbO and Fe2O3·1.2H2O, respectively. In the leachate, Mo existed primarily as Mo7O246−, HMo7O245−, and MoO42−. This study presents an environmentally friendly process for extracting Mo from molybdenum calcine.
{"title":"An investigation into the sodium molybdate leaching of molybdenum calcine","authors":"Jiayu Mi , Xingyu Chen , Ailiang Chen , Xuheng Liu , Jiangtao Li , Lihua He , Fenglong Sun , Zhongwei Zhao","doi":"10.1016/j.hydromet.2025.106553","DOIUrl":"10.1016/j.hydromet.2025.106553","url":null,"abstract":"<div><div>The ammonia leaching-purification-crystallization process is the conventional treatment method of molybdenum calcine. This process generates large amounts of nitrogen-containing wastewater and exhaust gases. Based on the self-coordination principle of Mo, where MoO<sub>3</sub> with low-polymerization ability combines with Na<sub>2</sub>MoO<sub>4</sub> into highly polymerized polymolybdates, this study proposes a novel, green leaching process using Na<sub>2</sub>MoO<sub>4</sub> for the selective extraction of Mo from molybdenum calcine. Leaching conditions were optimized, and the reaction mechanism was elucidated through the identification of solids using XRD, EDS mapping, XPS, and Raman spectroscopy. Results show that under optimal conditions, the leaching efficiency reached 98.6 %. Molybdenum from MoO<sub>3</sub>, PbMoO<sub>4</sub>, and FeMoO<sub>4</sub> phases in the calcine was effectively extracted, while Fe and Pb oxides remained in the leach residue as PbO and Fe<sub>2</sub>O<sub>3</sub>·1.2H<sub>2</sub>O, respectively. In the leachate, Mo existed primarily as Mo<sub>7</sub>O<sub>24</sub><sup>6−</sup>, HMo<sub>7</sub>O<sub>24</sub><sup>5−</sup>, and MoO<sub>4</sub><sup>2−</sup>. This study presents an environmentally friendly process for extracting Mo from molybdenum calcine.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"237 ","pages":"Article 106553"},"PeriodicalIF":4.8,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144886127","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 : 2025-11-01Epub Date: 2025-07-26DOI: 10.1016/j.hydromet.2025.106549
Dongfeng Zhou , Shuai Rao , Xingbin Li , Niangao Teng , Zhigan Deng , Hongyang Cao , Dongxing Wang , Zhiyuan Ma , Zhiqiang Liu
Industrial extraction of Ga and Ge from zinc concentrate has been achieved; however, their recoveries remain relatively low because of dispersion during various procedures. This study thoroughly investigated the distribution behavior and precipitation mechanism of Ga and Ge from zinc pressure leachate into refinery residue. Process mineralogical investigations demonstrated that Ga primarily precipitated through the formation of jarosite, while Ge enrichment was driven by reduction using zinc powder. Controlling the terminal acidity within the range of 6.0–7.0 g/L during pre-neutralization effectively minimized jarosite formation, thereby reducing Ga loss to below 2.0 mg/L. The cementation process was further improved by introducing secondary zinc oxide, followed by zinc powder in a sequential manner. Strategic adjustment of the pH profile—beginning at 1.9–2.1 and concluding at 3.0–3.5—led to residual Ga and Ga concentrations of less than 2.0 mg/L and 1.0 mg/L, respectively. These conditions enabled production trials to achieve recovery efficiencies above 85 % for Ga and over 96 % for Ge.
{"title":"Enhanced gallium and germanium recovery from zinc pressure leachate via zinc powder cementation","authors":"Dongfeng Zhou , Shuai Rao , Xingbin Li , Niangao Teng , Zhigan Deng , Hongyang Cao , Dongxing Wang , Zhiyuan Ma , Zhiqiang Liu","doi":"10.1016/j.hydromet.2025.106549","DOIUrl":"10.1016/j.hydromet.2025.106549","url":null,"abstract":"<div><div>Industrial extraction of Ga and Ge from zinc concentrate has been achieved; however, their recoveries remain relatively low because of dispersion during various procedures. This study thoroughly investigated the distribution behavior and precipitation mechanism of Ga and Ge from zinc pressure leachate into refinery residue. Process mineralogical investigations demonstrated that Ga primarily precipitated through the formation of jarosite, while Ge enrichment was driven by reduction using zinc powder. Controlling the terminal acidity within the range of 6.0–7.0 g/L during pre-neutralization effectively minimized jarosite formation, thereby reducing Ga loss to below 2.0 mg/L. The cementation process was further improved by introducing secondary zinc oxide, followed by zinc powder in a sequential manner. Strategic adjustment of the pH profile—beginning at 1.9–2.1 and concluding at 3.0–3.5—led to residual Ga and Ga concentrations of less than 2.0 mg/L and 1.0 mg/L, respectively. These conditions enabled production trials to achieve recovery efficiencies above 85 % for Ga and over 96 % for Ge.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"237 ","pages":"Article 106549"},"PeriodicalIF":4.8,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724945","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}