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Extraction of Se and Te from copper anode slime through pressure oxidation, atmospheric H2SO4 leaching and reduction with sulfur dioxide and copper powder 加压氧化、常压H2SO4浸出、二氧化硫和铜粉还原从铜阳极泥中提取Se和Te
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2025-12-01 Epub Date: 2025-08-27 DOI: 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.
常规H2SO4压力浸出铜阳极泥的硒提取效率有限,主要原因是元素硒的析出不理想。为了解决这一挑战,本研究开发了一种结合水热相变、大气H2SO4浸出和逐步还原的创新顺序工艺。利用E-pH图的热力学分析揭示了Cu2Se通过中间相CuSeO3·2H2O逐步转化为可溶的H2SeO3,而碲则通过中间相TeO2从Cu2Te进化为Te(OH)3+。在最优条件下,水热转化-大气浸出一体化工艺的Cu、Se、Te提取率分别为98.9%、98.3%和94.8%。随后从所得渗滤液中回收硒和碲,采用逐步还原和净化,最终产品的硒纯度分别为98.4% wt%和99.1% wt% Te。
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引用次数: 0
Impact of firing temperature and atmosphere on the chemical reactivity of UO2+x powders in nitric acid 烧制温度和气氛对UO2+x粉末在硝酸中化学反应性的影响
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2025-12-01 Epub Date: 2025-08-28 DOI: 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。
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引用次数: 0
Selective leaching of arsenic from zinc oxide dust in NaOH-(NH2)2CS solution NaOH-(NH2)2CS溶液中氧化锌粉尘中砷的选择性浸出
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2025-12-01 Epub Date: 2025-09-29 DOI: 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.
锌冶炼粉尘中砷的选择性脱除是资源回收和环境保护的重要措施。采用硫脲辅助碱性浸出法从锌冶炼粉尘中选择性提取砷。首先研究了砷溶解的热力学。考察了碱浸过程中NaOH浓度、硫脲浓度、浸出温度、浸出时间和液固比对砷锌浸出的影响。结果表明,硫脲的加入可有效地将砷的浸出率从58.1%提高到77.1%,同时抑制锌的浸出率从18.4%降低到2.6%。在最佳条件下,As、Zn、Fe、Pb、In和Ag的浸出效率分别为77.1%、2.6%、4.5%、2.1%、1.3%和3.2%,证实了砷对其他元素的选择性浸出。XRD、SEM和XPS表征表明,硫脲通过向溶液中释放S2−,促进了不溶性砷酸盐矿物的溶解,促进了ZnS和PbS沉淀的形成。该工艺有效地减少了锌、铅等贵重金属的损失。该方法可用于选择性地去除含砷氧化粉尘中的砷。
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引用次数: 0
Advancements in siderophore-based technologies for metal biorecovery 基于铁载体的金属生物回收技术的进展
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2025-12-01 Epub Date: 2025-08-20 DOI: 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.
铁载体是一种低分子量的金属螯合生物代谢物,具有高选择性结合铁和其他金属离子的能力。目前已经发现了500多种结构不同的铁载体,为潜在的金属络合提供了不同的配位机制。最近的研究主要在实验室条件下调查了它们在从初级和次级来源(包括矿石、矿山尾矿、电子废物和工业废水)中提取金属方面的应用。这篇综述对各种金属-铁载体系统的研究结果进行了严格的审查,评估了浸出参数、与助溶剂的协同使用以及与混合方法的整合等因素。然而,目前还没有商业应用,而且重大的经济和技术障碍——特别是高生产成本和可扩展性挑战——限制了实际可行性。本综述旨在巩固当前的科学认识,突出现有的局限性,并概述未来现实的研究方向,重点是克服技术和经济限制,以更广泛地实施。
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引用次数: 0
The effect and implication of impurities on the calcination of α spodumene for lithium extraction 杂质对α锂辉石煅烧提锂的影响及意义
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2025-12-01 Epub Date: 2025-08-30 DOI: 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
研究了西澳大利亚太古宙北皮尔巴拉和伊尔加恩克拉通地区钠长石-锂辉石型伟晶岩的一套锂辉石样品,以评估锂辉石及其伴生脉石相中微量元素杂质对锂辉石热转化的影响。将天然的单斜α-锂辉石形式转化为方形的β-锂辉石形式,需要对锂辉石进行煅烧,使其更适合湿法冶金过程中锂的回收。锂辉石含有微量的铁(500-10,000 mg/kg),锰(200-1400 mg/kg)和其他微量元素杂质。原生脉石矿物学包括石英、钠钾长石和云母,次生蚀变主要为绢云母层状硅酸盐(白云母-锂云母、绿泥石/库克石混合物),相对于锂辉石,Fe、Mn、Mg和K含量不同。原生云母和次生云母在低于锂辉石转化温度(970-1100℃)的温度(<950℃)下进行热去羟基化。分解云母形成的熔体覆盖在表面并部分包裹了煅烧的锂辉石颗粒表面。长石在1060 ~ 1200℃分解,与锂辉石的转变相一致,也可能导致熔体的形成,这取决于长石的成分(钾长石、钠长石)。其他矿物污染物如黑云母、辉石、角闪石等的热降解也与α-向β-锂辉石相变相吻合。生成的包裹晶粒的熔体降低了α-β锂辉石的转化速率和随后从煅烧锂辉石中提取锂的能力。锂辉石中的原生Fe和Mn杂质以及锂辉石内部的云母杂质对降低α-γ-β锂辉石转化温度有显著作用。锂辉石不是强导热体,热蚀变过程中云母和锂辉石内部Fe和Mn氧化的高度放热反应影响了锂辉石的导热性,导致锂辉石颗粒内部的热传递增加,促进了锂辉石在较低温度下的热转化。然而,高铁和高锰含量(> ~ 0.5 wt%)的锂辉石颗粒煅烧后呈现黑色、开放的烧结区,并伴有细小(<5 μm)颗粒的生成和Fe/Mn氧化物颗粒的析出。煅烧炉中的烧结和细粒的生成将导致煅烧产物中锂的回收率降低。该研究说明了在选矿阶段尽量减少精矿中云母和长石成分的重要性,这可能会导致提取过程中锂回收率的降低。然而,与锂辉石蚀变相关的云母的精细整合性质以及与锂辉石内部细裂缝相关的云母性质,如果在煅烧过程之前没有昂贵的精细研磨和清洗过程,则不太可能被释放出来。针对降低脉石物料对熟料形成和锂辉石颗粒包封影响的替代焙烧工艺是可行的,并进行了讨论。
{"title":"The effect and implication of impurities on the calcination of α spodumene for lithium extraction","authors":"Mark G. Aylmore,&nbsp;Martin A. Wells,&nbsp;Zakaria Quadir,&nbsp;William D.A. Rickard,&nbsp;Kai Rankenburg,&nbsp;Brent I.A. McInnes","doi":"10.1016/j.hydromet.2025.106570","DOIUrl":"10.1016/j.hydromet.2025.106570","url":null,"abstract":"&lt;div&gt;&lt;div&gt;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.&lt;/div&gt;&lt;div&gt;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.&lt;/div&gt;&lt;div&gt;Primary and secondary mica undergo thermal dehydroxylation at temperatures (&lt;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.&lt;/div&gt;&lt;div&gt;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.&lt;/div&gt;&lt;div&gt;However, calcined spodumene particles with high Fe and Mn contents (&gt; ∼ 0.5 wt%) showed black, open sintered regions, accompanied by the generation of fine (&lt;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.&lt;/div&gt;&lt;div&gt;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}
引用次数: 0
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 从黄铜矿中可持续回收铜:作为绿色浸出介质的共晶溶剂、原位电沉积和吸附剂改性平台:零废物过程的初步尝试
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2025-12-01 Epub Date: 2025-08-22 DOI: 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。
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引用次数: 0
Role of arsenic(V) and bismuth in the recovery of antimony by hydrolysis and precipitation from eluates produced during copper electrorefining 砷(V)和铋在铜电精炼过程中水解和沉淀法回收锑中的作用
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2025-11-01 Epub Date: 2025-07-24 DOI: 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.
从侧流中回收锑是一项具有挑战性的工作,因为砷和铋等杂质会影响提取效率和产品质量。本研究考察了As和Bi对铜电精炼过程中产生的洗脱液中锑水解的单独和联合影响。对合成和工艺洗脱液进行分析,以优化操作条件并了解杂质相互作用。不同pH值(0.25-0.9)的水解实验表明,在无杂质条件下,最大限度地提高锑回收率(> 90%)的最佳pH范围(0.6-0.7)。砷使锑的回收率降低了8% - 13%,使沉淀不稳定并形成非晶相。铋引起了较小的还原(3% - 7%),但在As存在的情况下效果减弱,As主导了系统的化学反应。工艺洗脱液表现出更大的可变性,特别是在提取产量方面,强调需要根据工业基质验证基于合成溶液的发现。该研究为通过杂质管理优化锑回收提供了见解,并突出了将合成和工艺洗脱液分析相结合的价值。
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引用次数: 0
Recovery of valuable metals from spent lithium-ion batteries based on a green and efficient leaching system of dimethyl-β-propionic acid thiophene (DMPT) 基于绿色高效二甲基β-丙酸噻吩(DMPT)浸出系统回收废旧锂离子电池中有价金属
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2025-11-01 Epub Date: 2025-08-13 DOI: 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.
废旧锂离子电池的回收利用代表着新能源产业链的终端阶段,在资源节约和环境保护方面具有举足轻重的作用。尽管越来越受到重视,但制定绿色和有效的回收战略仍然是一项重大挑战。近年来,各种环境友好型溶剂——包括超临界流体、深度共晶溶剂(DES)和离子液体(ILs)——被用于促进锂离子电池的可持续回收利用。其中,生物质衍生试剂(BDRs)因其可再生和低环境影响而成为一种有前景的应用方法。在这项研究中,提出了一种新的浸出策略,利用天然有机分子二甲基β-丙酸噻吩(DMPT)从废旧三元锂电池阴极中高效环保地回收有价金属。利用DMPT结构中固有的羧基官能团和氯离子的协同作用,Li、Ni、Co和Mn的浸出效率分别达到98.7%、97.2%、97.8%和98.3%。采用x射线衍射(XRD)、扫描电镜(SEM)和x射线光电子能谱(XPS)对浸出反应和产物进行了系统的研究。与传统的湿法冶金工艺相比,这种基于dmpt的方法不需要强酸、强碱或额外的还原剂,从而最大限度地减少了二次污染。所提出的方法为从废lib中回收关键金属提供了一种绿色、可持续和有效的替代方法,并且在未来的工业应用中具有巨大的潜力。
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引用次数: 0
An investigation into the sodium molybdate leaching of molybdenum calcine 钼煅烧物的钼酸钠浸出试验研究
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2025-11-01 Epub Date: 2025-08-19 DOI: 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.
氨浸—净化—结晶工艺是钼煅烧的常规处理方法。这一过程产生大量含氮废水和废气。本研究基于Mo的自配位原理,即低聚合能力的MoO3与Na2MoO4结合形成高聚合的多钼酸盐,提出了采用Na2MoO4选择性提取钼煅烧物中Mo的绿色浸出新工艺。对浸出条件进行了优化,并利用XRD、EDS作图、XPS和拉曼光谱对固体进行了鉴定,阐明了反应机理。结果表明,在最佳浸出条件下,浸出率可达98.6%。煅烧物中MoO3、PbMoO4和FeMoO4相中的钼被有效萃取,而Fe和Pb氧化物分别以PbO和Fe2O3·1.2H2O的形式留在浸出渣中。在渗滤液中,Mo主要以Mo7O246−、HMo7O245−和MoO42−的形式存在。研究了一种从钼煅烧物中提取钼的环保工艺。
{"title":"An investigation into the sodium molybdate leaching of molybdenum calcine","authors":"Jiayu Mi ,&nbsp;Xingyu Chen ,&nbsp;Ailiang Chen ,&nbsp;Xuheng Liu ,&nbsp;Jiangtao Li ,&nbsp;Lihua He ,&nbsp;Fenglong Sun ,&nbsp;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}
引用次数: 0
Enhanced gallium and germanium recovery from zinc pressure leachate via zinc powder cementation 锌粉胶结法提高锌压渗滤液中镓锗的回收率
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2025-11-01 Epub Date: 2025-07-26 DOI: 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.
从锌精矿中实现了镓和锗的工业提取;然而,由于在各种程序中的分散,它们的回收率仍然相对较低。研究了锌压渗滤液中Ga和Ge在炼油厂废渣中的分布行为和沉淀机理。工艺矿物学研究表明,Ga主要通过黄钾铁矾的形成沉淀,而Ge的富集则是由锌粉的还原作用驱动的。在预中和过程中,将终端酸度控制在6.0 ~ 7.0 g/L范围内,可以有效地减少黄钾铁矾的形成,从而将Ga损失降低到2.0 mg/L以下。通过引入二次氧化锌,再依次引入锌粉,进一步改进了胶结工艺。战略性地调整pH分布(从1.9-2.1开始,到3.0 - 3.5结束)导致残留Ga和Ga浓度分别小于2.0 mg/L和1.0 mg/L。这些条件使得生产试验的回收率达到了85%以上的Ga和96%以上的Ge。
{"title":"Enhanced gallium and germanium recovery from zinc pressure leachate via zinc powder cementation","authors":"Dongfeng Zhou ,&nbsp;Shuai Rao ,&nbsp;Xingbin Li ,&nbsp;Niangao Teng ,&nbsp;Zhigan Deng ,&nbsp;Hongyang Cao ,&nbsp;Dongxing Wang ,&nbsp;Zhiyuan Ma ,&nbsp;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}
引用次数: 0
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Hydrometallurgy
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