Hydrometallurgy最新文献_第9页

Choline chloride-lactic acid-ascorbic acid (ChCl-LA-AA) based green deep eutectic solvent for leaching LiMn2O4 cathode material of spent Li-ion batteries 氯化胆碱-乳酸-抗坏血酸（ChCl-LA-AA）基绿色深共晶溶剂浸出废锂离子电池正极材料LiMn2O4

IF 4.8 2区材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING

Hydrometallurgy

Pub Date : 2025-07-07 DOI: 10.1016/j.hydromet.2025.106529

Jasreen Kaur Jasmel Singh , Masud Rana , Md Ishtiaq Hossain Khan , Young Tae Jo, Jeong-Hun Park

The application of lithium manganese oxide (LMO) as a cathode material in Li-ion batteries (LIBs) is increasing due to its affordability, safety, nontoxicity, and high energy storage capabilities. Although its use in electric vehicles (EVs) and portable devices is proliferating, research on recycling valuable metals from spent batteries of this type remains limited. Therefore, this study investigates the recycling of lithium (Li) and manganese (Mn) from spent LiMn₂O₄ cathode materials using a choline chloride and lactic acid (ChCl-LA) deep eutectic solvent (DES) in the presence of various reducing agents such as ascorbic acid (AA), glucose, and formic acid (FA). The compositions of the spent cathode LiMn₂O₄ material, solid residue, and the leachate obtained post-leaching were analyzed using ICP-OES, XPS, SEM-EDS, and XRD analyses. Results indicated that about 100 % leaching efficiencies of both Li and Mn metals were achieved at 90 °C, 1 h, 20 g/L solid-to-liquid ratio and a 1:2:1 M ratio of ChCl-LA-AA. The XRD analysis results showed the presence of minor peaks of manganese oxide in the solid residues obtained from glucose and FA leaching, while the LiMn₂O₄ peaks are absent after the treatment of AA, confirming the effective extraction of metallic elements. Meanwhile, the SEM-EDS analysis showed the raw LiMn₂O₄ material had agglomerated nanoparticles, while the solid residues exhibited increased porosity and reduced Mn content (26.1 wt% for glucose and 23.9 wt% for FA). The solid residue obtained after leaching with AA showed a significant increase in carbon content (82.1 %) and a decrease in Mn (1.42 %). The XPS spectra further confirmed the reduction of manganese (III) or manganese (IV) oxidation states into manganese (II) state and almost complete leaching of Mn and Li. Finally, a detailed mechanism for Mn and Li leaching from the spent LiMn₂O₄ was proposed. The recycling process applied in this study is shown to be feasible and promising for broader application.

锂锰氧化物（LMO）作为锂离子电池（LIBs）正极材料的应用越来越多，因为它具有可负担性、安全性、无毒性和高能量存储能力。尽管它在电动汽车（ev）和便携式设备中的应用正在激增，但从这类废旧电池中回收有价值金属的研究仍然有限。因此，本研究研究了在各种还原剂如抗坏血酸（AA）、葡萄糖和甲酸（FA）的存在下，使用氯化胆碱和乳酸（ChCl-LA）深度共晶溶剂（DES）从废LiMn2O4正极材料中回收锂（Li）和锰（Mn）。利用ICP-OES、XPS、SEM-EDS和XRD分析了废阴极LiMn2O4材料、固体残渣和浸出液的组成。结果表明，在90℃、1 h、料液比20 g/L、ChCl-LA-AA浓度为1:2:1的条件下，Li和Mn金属的浸出效率均达到100%左右。XRD分析结果表明，葡萄糖和FA浸出的固体残渣中存在少量的氧化锰峰，而AA处理后没有出现LiMn2O4峰，证实了金属元素的有效提取。同时，SEM-EDS分析表明，原始LiMn2O4材料具有团聚的纳米颗粒，而固体残留物的孔隙率增加，Mn含量降低（葡萄糖为26.1% wt%， FA为23.9%）。AA浸出后得到的固体渣碳含量显著增加（82.1%），Mn含量显著降低（1.42%）。XPS光谱进一步证实锰（III）或锰（IV）氧化态还原为锰（II）态，Mn和Li几乎完全浸出。最后，提出了从废LiMn2O4中浸出Mn和Li的详细机理。本研究采用的回收工艺是可行的，具有广阔的应用前景。

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引用次数: 0

Arsenic precipitation and bioscorodite crystallization from acidic metallurgical wastewater under different bioreactor schemes: In-silico performance analysis 不同生物反应器方案下酸性冶金废水中的砷沉淀和生物云母结晶：硅性能分析

IF 4.8 2区材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING

Hydrometallurgy

Pub Date : 2025-07-04 DOI: 10.1016/j.hydromet.2025.106531

Evelyn Gaxiola-Muñiz , Ricardo Aguilar-López , Sergio A. Medina-Moreno , Edgar N. Tec-Caamal

Arsenic removal from water is still a challenge to overcome, and the biologically induced formation of scorodite offers an effective approach for treating arsenic-containing effluents from the metallurgical industry. This paper presents a model-based analysis of the dynamics of the overall bioscorodite process under different bioreactor schemes. For this purpose, a modified model was experimentally validated obtaining 0.87 < R² < 0.99 for all variables with p-values <0.001. The validated model was able to adequately predict the dynamics of each variable, which were verified by experimental observations. Subsequently, batch, fed-batch, combined batch/continuous, single-stage, and multi-stage continuous bioreactors were investigated through simulations, testing operational variables that influence the arsenic removal capacity, such as inoculum, ion concentration, dilution rate, and seeding. A comparative basis was then established to identify the bioreactor setups that enhance the arsenic immobilization as a bioscorodite. Single-stage and cascade bioreactors had high arsenic precipitation rates (up to 3.2 g L⁻¹ d⁻¹) and crystal sizes around ∼150 μm. Results showed that three reactors connected in series were able to precipitate 87 % arsenic with a high fed concentration (6.2 g L⁻¹), while a higher number of serial reactors may increase conversion but affect negatively the practicality and feasibility of the system. Combined batch/continuous scheme was useful to obtain large crystal sizes, up to 225 μm. These findings underscore the effectiveness of a model-based design for bioscorodite crystallization process, providing a promising and scalable solution for arsenic removal from industrial effluents.

从水中去除砷仍然是一个需要克服的挑战，而生物诱导形成铁球石为处理冶金工业含砷废水提供了一种有效的方法。本文提出了一个基于模型的动态分析的整体生物云母过程在不同的生物反应器方案。为此，对修正模型进行了实验验证，得到0.87 <；R2 & lt;p值为<；0.001的所有变量均为0.99。验证后的模型能够充分预测各变量的动态，并通过实验观察进行了验证。随后，通过模拟研究了间歇、补料间歇、间歇/连续组合、单级和多级连续生物反应器，测试了影响砷去除能力的操作变量，如接种量、离子浓度、稀释率和播种。然后建立了一个比较基础，以确定生物反应器设置，以提高砷作为生物污泥的固定化。单级和梯级生物反应器具有较高的砷沉淀率（高达3.2 g L−1 d−1），晶体尺寸约为~ 150 μm。结果表明，3个串联反应器可在高进料浓度（6.2 g L−1）下沉淀87%的砷，较高的串联反应器数量可能会提高转化率，但不利于系统的实用性和可行性。间歇式/连续式组合方案可获得大尺寸晶体，最高可达225 μm。这些发现强调了基于模型设计的生物蛭石结晶过程的有效性，为工业废水中的砷去除提供了一种有前途的可扩展解决方案。

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引用次数: 0

Precipitation of rare earth phosphates through apatite leach as by-product of nitrophos acid from unconventional phosphate deposit of carbonatite, Malakand, Pakistan 巴基斯坦马拉坎德碳酸盐岩非常规磷矿硝磷副产物磷灰石浸出沉淀稀土磷酸盐

IF 4.8 2区材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING

Hydrometallurgy

Pub Date : 2025-07-03 DOI: 10.1016/j.hydromet.2025.106530

Farva Arshad , Munirah Atique Khan , Attiqa Nasir , Muhammad Haider Ali , Lubna Basit , Muhammad Nasir Siddique , Muhammad Nadeem

The igneous carbonatite apatite ore of Sellai Patti (Malakand, Pakistan) was beneficiated through mineral processing methods (crushing, grinding, gravity separation, and magnetic separation). The concentrate [Ca₅(PO₄)₃, F] (30 % P₂O₅, 0.7 % REEs) was leached with 65 % nitric acid (S/L 0.42, 65 °C, 700 rpm). The leachate (2.78 g/L REEs, 154 g/L P₂O₅) yielded a 92 % recovery of REEs. Precipitation of REEs was performed with 33 % ammonia solution by two different methods. The direct precipitation process (DPP), produced REE precipitates (34 %) at a pH of 0.2–0.5 with a subsequent hot washing. The remaining filtrate, after precipitation, contained REEs at a low concentration of 0.2 g/L, 97 g/L P₂O₅ and calcium up to 102 g/L. In the nitrophos precipitation process (NPP), a pre-concentration of REEs from 2.8 g/L to 4.1 g/L was observed through the removal of dissolved calcium in the form of calcium nitrate tetrahydrate (CNTH) as a result of freezing the leachate at −20 °C. The precipitates (9 % REEs) obtained at pH 1.7 followed by its re-dissolution in 65 % nitric acid (S/L 1:10) and overnight recrystallization with 50 % excess oxalic acid enhanced REEs concentration up to 30 %. The leftover nitrophos acid (NP acid), a precursor of nitrophos fertilizer, contained only <1 mg/L of REEs, 135 g/L of P₂O₅, and up to 40 g/L of calcium. The present research advances a sustainable and efficient methodology for the extraction of REEs through an innovative and significantly effective DPP.

采用破碎、磨矿、重选、磁选等选矿方法对Sellai Patti （Malakand, Pakistan）火成岩碳酸盐岩磷灰石矿石进行了选矿。用65%的硝酸（S/L 0.42, 65℃，700 rpm）浸出精矿[Ca5(PO4)3, F] （30% P2O5, 0.7% REEs）。该渗滤液（稀土2.78 g/L, P2O5 154 g/L）稀土回收率为92%。用两种不同的方法在33%的氨溶液中进行了稀土元素的沉淀。直接沉淀法（DPP）在pH为0.2 ~ 0.5的条件下产生稀土析出物（34%），随后进行热洗。沉淀后的滤液中稀土含量为0.2 g/L， P2O5含量为97 g/L，钙含量为102 g/L。在硝基磷沉淀过程（NPP）中，通过去除四水合硝酸钙（CNTH）形式的溶解钙，在−20°C冻结渗滤液，观察到稀土的预浓度从2.8 g/L到4.1 g/L。在pH为1.7的条件下得到9%的稀土析出物，然后在65%的硝酸（S/L 1:10）中再溶解，用过量50%的草酸过夜再结晶，稀土浓度提高到30%。硝基磷肥的前体硝基磷酸（NP酸）残留的稀土含量仅为1mg /L， P2O5含量为135g /L，钙含量高达40g /L。本研究提出了一种可持续和高效的方法，通过创新和显著有效的DPP提取稀土。

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引用次数: 0

Leaching kinetics of molybdenite with layered structure and hydrophobic properties in the H2SO4-H2O2-H2O system at atmospheric pressure 层状疏水性辉钼矿在常压H2SO4-H2O2-H2O体系中的浸出动力学

IF 4.8 2区材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING

Hydrometallurgy

Pub Date : 2025-07-03 DOI: 10.1016/j.hydromet.2025.106527

Zhiyuan Chen , Zihui Jiang , Qiu Hu , Jiangtao Li

Previous studies on the leaching kinetics of molybdenite were primarily based on processing data using a contraction core model with spherical mineral particles. However, molybdenite particles exhibit a thin plate and layered structure. In this study, a model of circular particles was employed to derive the kinetic equation. The apparent activation energies of the molybdenite leaching reaction, both without mechanical activation and with mechanical activation treatment, were calculated as 55.3 kJ/mol and 49.5 kJ/mol, respectively. The layered structure of molybdenite renders its mineral particles challenging to grind during the ball milling process. Nonetheless, this process enhanced the active point of the mineral to a certain extent, thereby facilitating the leaching reaction. The rate-limiting step of the leaching reaction was identified as the chemical reaction step. Specifically, the reaction order of H₂SO₄ and H₂O₂ were determined as 0.063 and 0.959, respectively. Notably, variations in the H₂O₂ concentration exerted a significant impact on the leaching effect, while changes in the concentration of H₂SO₄ exhibited a relatively smaller effect. Additionally, molybdenite exhibited strong hydrophobic properties. The addition of surfactants improved the reaction environment and enhanced the leaching effect. The expression for leaching kinetics was defined as follows:

1 - \sqrt{1 - α} = k_{r} t = 7.73 \times 10^{3} r_{0}^{- 1} C_{H 2 SO 4}^{0.063} C_{H 2 O 2}^{0.959} e^{- \frac{59706}{RT}} t

以往对辉钼矿浸出动力学的研究主要基于球形矿物颗粒收缩岩心模型的处理数据。辉钼矿颗粒呈薄板状和层状结构。在本研究中，采用圆形粒子模型推导了动力学方程。经计算，未经机械活化和经过机械活化处理的辉钼矿浸出反应的表观活化能分别为55.3 kJ/mol和49.5 kJ/mol。辉钼矿的层状结构使其矿物颗粒在球磨过程中难以研磨。但该过程在一定程度上提高了矿物的活性点，有利于浸出反应的进行。确定浸出反应的限速步骤为化学反应步骤。其中，H2SO4和H2O2的反应阶数分别为0.063和0.959。值得注意的是，H2O2浓度的变化对浸出效果影响显著，而H2SO4浓度的变化对浸出效果的影响相对较小。辉钼矿具有较强的疏水性。表面活性剂的加入改善了反应环境，提高了浸出效果。浸出动力学表达式定义为：1−1−α=krt=7.73×103r0−1CH2SO40.063CH2O20.959e−59706RTt

{"title":"Leaching kinetics of molybdenite with layered structure and hydrophobic properties in the H2SO4-H2O2-H2O system at atmospheric pressure","authors":"Zhiyuan Chen , Zihui Jiang , Qiu Hu , Jiangtao Li","doi":"10.1016/j.hydromet.2025.106527","DOIUrl":"10.1016/j.hydromet.2025.106527","url":null,"abstract":"<div><div>Previous studies on the leaching kinetics of molybdenite were primarily based on processing data using a contraction core model with spherical mineral particles. However, molybdenite particles exhibit a thin plate and layered structure. In this study, a model of circular particles was employed to derive the kinetic equation. The apparent activation energies of the molybdenite leaching reaction, both without mechanical activation and with mechanical activation treatment, were calculated as 55.3 kJ/mol and 49.5 kJ/mol, respectively. The layered structure of molybdenite renders its mineral particles challenging to grind during the ball milling process. Nonetheless, this process enhanced the active point of the mineral to a certain extent, thereby facilitating the leaching reaction. The rate-limiting step of the leaching reaction was identified as the chemical reaction step. Specifically, the reaction order of H<sub>2</sub>SO<sub>4</sub> and H<sub>2</sub>O<sub>2</sub> were determined as 0.063 and 0.959, respectively. Notably, variations in the H<sub>2</sub>O<sub>2</sub> concentration exerted a significant impact on the leaching effect, while changes in the concentration of H<sub>2</sub>SO<sub>4</sub> exhibited a relatively smaller effect. Additionally, molybdenite exhibited strong hydrophobic properties. The addition of surfactants improved the reaction environment and enhanced the leaching effect. The expression for leaching kinetics was defined as follows:<span><span><span><math><mn>1</mn><mo>−</mo><msqrt><mrow><mn>1</mn><mo>−</mo><mi>α</mi></mrow></msqrt><mo>=</mo><msub><mi>k</mi><mi>r</mi></msub><mi>t</mi><mo>=</mo><mn>7.73</mn><mo>×</mo><msup><mn>10</mn><mn>3</mn></msup><msubsup><mi>r</mi><mn>0</mn><mrow><mo>−</mo><mn>1</mn></mrow></msubsup><msubsup><mi>C</mi><mrow><mi>H</mi><mn>2</mn><mi>SO</mi><mn>4</mn></mrow><mn>0.063</mn></msubsup><msubsup><mi>C</mi><mrow><mi>H</mi><mn>2</mn><mi>O</mi><mn>2</mn></mrow><mn>0.959</mn></msubsup><msup><mi>e</mi><mrow><mo>−</mo><mfrac><mn>59706</mn><mi>RT</mi></mfrac></mrow></msup><mi>t</mi></math></span></span></span></div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"236 ","pages":"Article 106527"},"PeriodicalIF":4.8,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144572672","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Study of hydrogen gas formation during leaching of weakly radioactive ores of the Tomtor deposit: Geo-radiochemical nature of the reducing properties of the ore 托托尔矿床弱放射性矿石浸出过程中氢气形成的研究：矿石还原性的地球放射化学性质

IF 4.8 2区材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING

Hydrometallurgy

Pub Date : 2025-06-26 DOI: 10.1016/j.hydromet.2025.106523

Vladimir I. Kuzmin, Dmitrii V. Kuzmin, Oleg A. Epov, Timur Yu. Ivanenko

Direct alkaline leaching of weakly radioactive rare metal ores of the Tomtor deposit (Russia) was investigated. It was found that the process of leaching monazite with sodium hydroxide solutions in the presence of various associated mineral components is accompanied by the release of significant amounts of hydrogen and the formation of stable foam filling the reactor and preventing the elimination of hazardous gas. The discovered phenomenon is unique, since hydrogen release occurs at a high rate even at low temperatures (40–50 °C) and when leaching ores in both alkaline and acidic environments (hydrofluoric acid solutions). It is assumed that the high reduction potential of the ores is associated with the deaeration of mineral components (oxygen removal) during their long-term radiochemical irradiation. Preliminary studies using solid-state NMR confirmed this assumption. A significant amount of hydride ions, which are part of stable mixed cluster compounds of aluminum oxides and phosphates, were found in ore samples. It is assumed that the high stability of the foam formed in this process is due to the formation of a structural and mechanical barrier of hydrophobic pulp particles, including un-decomposed pyrite. Undesirable foaming is eliminated by adding an anionic surfactant (sodium stearate) to the pulp, which ensures the removal of hydrophobic particles from the surface of gas bubbles.

对俄罗斯托托矿床弱放射性稀有金属矿石进行了直接碱浸试验。研究发现，在各种伴合矿物成分存在的情况下，用氢氧化钠溶液浸出独居石的过程伴随着大量氢气的释放，并形成稳定的泡沫填充反应器，阻止了有害气体的消除。所发现的现象是独特的，因为即使在低温（40-50°C）和在碱性和酸性环境（氢氟酸溶液）中浸出矿石时，氢的释放速度也很高。假定矿石的高还原潜力与长期放射化学照射期间矿物成分的脱氧（除氧）有关。使用固态核磁共振进行的初步研究证实了这一假设。在矿石样品中发现了大量的氢化物离子，氢化物离子是氧化铝和磷酸盐稳定混合簇化合物的一部分。假设在此过程中形成的泡沫具有高稳定性是由于疏水纸浆颗粒（包括未分解的黄铁矿）形成了结构和机械屏障。通过在纸浆中添加阴离子表面活性剂（硬脂酸钠）来消除不希望的泡沫，这确保了从气泡表面去除疏水颗粒。

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引用次数: 0

The use of hydrophobic deep eutectic solvent dodecanoic acid/menthol as a sustainable diluent for the continuous extraction process of Fe and Ti separation 采用疏水深度共熔溶剂十二烷酸/薄荷醇作为持续稀释剂，进行了Fe和Ti分离的连续萃取过程

IF 4.8 2区材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING

Hydrometallurgy

Pub Date : 2025-06-25 DOI: 10.1016/j.hydromet.2025.106526

Nikita A. Milevskii, Dmitriy V. Lobovich, Arina V. Milevskaya, Yulia A. Zakhodyaeva, Andrey A. Voshkin

Hydrophobic deep eutectic solvents (HDES) have long been used for the extraction of metal ions from aqueous systems. This study proposes the use of HDES composed of dodecanoic acid and menthol as a diluent for tributyl phosphate (TBP), which serves as the extractant. The results demonstrate that the extraction system developed remains stable across a broad range of TBP concentrations and possesses excellent physical properties, making it suitable for laboratory-scale extraction equipment. By examining the extraction of iron and titanium ions, key dependencies of extraction efficiency were identified as varying acidity levels, volume ratios, initial metal concentrations and conditions for effective stripping. Notably, the efficiency of the extractant remained unchanged after ten cycles of extraction and stripping, particularly for titanium ions extracted from 10 mol/L hydrochloric acid. This indicates the chemical stability of the proposed extraction system. A continuous separation process for iron and titanium was successfully implemented on laboratory extraction equipment using liquid pseudomembranes, achieving an efficiency greater than 95 % of the theoretical maximum. These findings suggest that HDES have significant potential for use as non-volatile, non-combustible and renewable solvents in extraction processes.

疏水深共晶溶剂（HDES）长期以来被用于从水体系中提取金属离子。本研究提出用十二烷酸和薄荷醇组成的HDES作为磷酸三丁酯（TBP）的稀释剂，作为萃取剂。结果表明，该萃取体系在较宽的TBP浓度范围内保持稳定，具有优异的物理性能，适合实验室规模的萃取设备。通过考察铁和钛离子的萃取，确定了萃取效率的关键依赖关系是不同的酸度水平、体积比、初始金属浓度和有效剥离的条件。值得注意的是，在10 mol/L的盐酸中提取钛离子后，萃取剂的萃取效率保持不变。这表明了所提萃取体系的化学稳定性。在实验室萃取设备上，利用液体假膜成功地实现了铁和钛的连续分离，效率大于理论最大值的95%。这些发现表明，HDES在萃取过程中作为非挥发性、不可燃和可再生溶剂具有巨大的潜力。

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引用次数: 0

Evaluating the effectiveness of iron oxide (Fe3O4) nanoparticles vs. traditional chloride methods for copper cementation and recovery from industrial waste solutions by aluminium 评价氧化铁（Fe3O4）纳米颗粒与传统氯化物方法在铜胶结和铝回收工业废液中的有效性

IF 4.8 2区材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING

Hydrometallurgy

Pub Date : 2025-06-25 DOI: 10.1016/j.hydromet.2025.106528

Cecilia Daniela Costa , María José Hernandez Triana , Mario Avila , Virginia Emilse Diz , Graciela Alicia González

The cementation of copper on aluminium is a well-studied process, typically facilitated by chloride ions to overcome the insulating aluminium oxide layer. This study presents an alternative approach using magnetite (Fe₃O₄) nanoparticles as electron (redox) mediators, allowing the cementation process to occur despite the presence of the aluminium oxide layer. After optimizing the concentration of the Fe₃O₄ suspension, the pH, and the reaction time, the performance of this method was compared to the classical chloride ion-based approach. The nanoparticle assisted method achieved higher recovery (%) of copper, but at a slower pace. This difference in reaction speed explains the more compact, non-oxidize copper deposits observed by SEM and DRX, in contrast to the dendritic and airy deposits with a high fraction of Cu₂O obtained using the classical chloride method. Under optimized conditions, the method was applied for the recovery of Cu from two industrial PCB solutions, achieving excellent recoveries after adjusting the pH.

铜在铝上的胶结是一个很好的研究过程，通常由氯离子来克服绝缘氧化铝层。这项研究提出了一种替代方法，使用磁铁矿（Fe₃O₄）纳米颗粒作为电子（氧化还原）介质，允许在存在氧化铝层的情况下发生胶结过程。通过优化Fe₃O₄悬浮液的浓度、pH和反应时间，将该方法的性能与经典的氯离子法进行了比较。纳米颗粒辅助方法获得了更高的铜回收率（%），但速度较慢。这种反应速度的差异解释了SEM和DRX观察到的更致密，非氧化的铜矿床，而不是用经典的氯化物方法获得的含有高分数Cu₂O的枝状和airy矿床。在优化的条件下，将该方法应用于两种工业PCB溶液中Cu的回收，调整pH后，回收率均达到了优异的水平。

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引用次数: 0

Recovery process of rare earths, Al, U, and Th from ionic rare earth purification residue using sequential alkaline leaching, acid leaching solvent extraction and stripping 顺序碱浸、酸浸、溶剂萃取、汽提从离子型稀土提纯渣中回收稀土、Al、U、Th的工艺研究

IF 4.8 2区材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING

Hydrometallurgy

Pub Date : 2025-06-24 DOI: 10.1016/j.hydromet.2025.106524

Qiaofa Lan , Xiaolin Zhang , Fei Niu , Donghui Liu , Youming Yang

Ionic rare earth purification residue (PR) originates from refining of ionic rare earth ores and is predominantly composed of rare earth elements (REEs), aluminum (Al), and silicon (Si). This is a recyclable secondary resource. It provides substantial challenges due to its classification as low-level radioactive waste (LLW). Recognizing the distinctive properties of PR, this paper describes a highly efficient process for the recovery and enrichment of Al, REEs, uranium (U), and thorium (Th) through a multistep process encompassing alkali digestion, hydrochloric acid leaching, sole extractant enrichment and separation. At a controlled temperature of 70 °C, the Al digestion efficiency reached 88.9 %. The alkali digestion residue underwent hydrochloric acid leaching, yielding leaching efficiencies of 99.9 %, 99.4 %, and 99.0 % for REEs, U(VI), and Th(IV), respectively. Notably, the amount of insoluble residue was reduced by 90 %, and it was transformed from LLW into general solid waste residue. Additionally, the utilization of 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester (HEHEHP) as the sole extractant provided 100 % extraction efficiencies for U(VI) and Th(IV). After stepwise stripping processes, the purities of both U(VI) and Th(IV) exceeded 90 %. The REEs were precipitated as RE₂(C₂O₄)₃ and subsequently calcined to produce rare earth oxides with a recovery of 90.1 % and a purity of 97.4 %. This comprehensive scheme addressed the persistent challenges associated with long-term storage and radiological environmental risk.

离子型稀土提纯渣（PR）是离子型稀土矿提纯后的产物，主要由稀土元素（ree）、铝（Al）和硅（Si）组成。这是一种可回收的二次资源。由于它被归类为低放射性废物（LLW），因此带来了巨大的挑战。认识到PR的独特性质，本文描述了一种通过碱消化、盐酸浸出、单萃取剂富集和分离等多步骤过程回收和富集Al、ree、铀(U)和钍（Th）的高效工艺。在70℃的控制温度下，铝的溶出效率达到88.9%。碱溶渣进行盐酸浸出，稀土、铀（VI）和钍（IV）的浸出效率分别为99.9%、99.4%和99.0%。值得注意的是，不溶性废渣的量减少了90%，并由LLW转化为一般固体废渣。此外，利用2-乙基己基膦酸单2-乙基己基酯（HEHEHP）作为唯一萃取剂，对U（VI）和Th（IV）的萃取效率为100%。分步溶出后，U（VI）和Th（IV）的纯度均超过90%。稀土元素以RE2(C2O4)3的形式析出，煅烧制得稀土氧化物，回收率为90.1%，纯度为97.4%。这一综合方案解决了与长期储存和辐射环境风险相关的持续挑战。

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引用次数: 0

Stepwise recovery of gallium (Ga), lithium (Li), and rare earth elements (REEs) from roasted coal gangue based on leaching kinetics differentiation 基于浸出动力学分异的焙烧煤矸石中镓（Ga）、锂（Li）和稀土元素（REEs）的分步回收

IF 4.8 2区材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING

Hydrometallurgy

Pub Date : 2025-06-24 DOI: 10.1016/j.hydromet.2025.106525

Jingzheng Wang , Hongxiang Xu , Yijun Cao , Kejia Ning , Biao Fu , Lin Ma , Xin Sun , Yuntao Kang , Mengting Hong , Guixia Fan , Xiahui Gui , Jiushuai Deng

Coal resources are a potential source of strategic metals. This study explores the leaching characteristics and mechanisms for extracting gallium (Ga), lithium (Li), and rare earth elements (REEs) from coal gangue under roasting and acid leaching conditions. Based on the differences in their leaching characteristics, a stepwise leaching strategy is proposed for efficient separation and recovery. Gallium and lithium are primarily associated with silicate minerals, while rare earth elements exist as independent rare earth minerals. Roasting at 600 °C enhances chemical reactivity, increasing the specific surface area and pore volume of the sample, thereby improving the leaching efficiency of Ga, Li, and REEs. The leaching of Ga and Li is mainly controlled by chemical reactions and is highly temperature-dependent, while the leaching of REEs follows a mixed control model. The stepwise extraction strategy involves leaching at 50 °C for 15 min to recover approximately 80 % of the REEs, with minimal loss of Ga and Li (∼7 %), followed by further leaching at 90 °C for 180 min to recover the remaining Ga and Li. This process demonstrates the potential of the stepwise extraction strategy for the efficient separation and recovery of these elements.

煤炭资源是战略金属的潜在来源。研究了在焙烧和酸浸条件下从煤矸石中提取镓（Ga）、锂（Li）和稀土元素（ree）的浸出特征和机理。根据其浸出特性的差异，提出了一种分步浸出策略，以实现有效的分离和回收。镓和锂主要与硅酸盐矿物伴生，而稀土元素作为独立的稀土矿物存在。600℃焙烧提高了化学反应性，增加了样品的比表面积和孔体积，从而提高了Ga、Li和ree的浸出效率。Ga和Li的浸出主要受化学反应控制，且高度依赖于温度，而稀土的浸出则遵循混合控制模式。分步提取策略包括在50°C下浸出15分钟，以回收约80%的稀土，Ga和Li的损失最小（~ 7%），然后在90°C下进一步浸出180分钟，以回收剩余的Ga和Li。这一过程证明了逐步萃取策略对这些元素的有效分离和回收的潜力。

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引用次数: 0

Recovery of transition metals (Ni, Co, and Mn) and Li from the sulfate leach solutions of spent ternary lithium-ion batteries by stepwise solvent extraction and precipitation 从废三元锂离子电池硫酸盐浸出液中分步萃取和沉淀法回收过渡金属（Ni、Co、Mn）和Li

IF 4.8 2区材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING

Hydrometallurgy

Pub Date : 2025-06-16 DOI: 10.1016/j.hydromet.2025.106519

Kuifang Zhang , Bohan Wei , Bin Zeng , Sen Qiu , Xiaocong Zhong , Ruixiang Wang

Sulfate leachate from spent ternary lithium-ion batteries (LIBs) contain valuable metals, such as transition metals (Ni, Co, and Mn) and Li, and impurity metals, such as Al and Fe. Selectively separating them from solutions is necessary for their recovery. In this work, a stepwise solvent extraction and precipitation process is proposed for the selective separation and recovery of transition metals (Ni, Co, and Mn) and Li from sulfate-leaching solutions of spent ternary lithium-ion batteries. First, 100 % of the impurity metals (Al and Fe) were selectively removed from the solution through a single-stage extraction using 22.5 % (v/v) N1923 in sulfonated kerosene at an O/A ratio of 1:1 for 10 min. The losses of the transition metals (Ni, Co, and Mn) and Li were only 1.65 %. The Al and Fe in the loaded organic system was completely stripped using a 1 mol/L HNO₃ solution, followed by regeneration with sodium carbonate solution. Subsequently, the raffinate (pH = 4.46) was directly used for the co-extraction of Ni, Co, and Mn by Cyanex 272. A five-stage countercurrent extraction was performed with an organic system consisting of 1 mol/L Cyanex 272 (saponification degree: 50 %) in sulfonated kerosene, using an O/A ratio of 2.25:1. Nearly all of the Ni, Co, and Mn were extracted, while only 1.43 % Li was co-extracted. The extracted Ni, Co, and Mn in the loaded organic system were completely stripped through five-stage counter-current stripping using 1 mol/L H₂SO₄ with an O/A ratio of 5:1. During the stepwise solvent extraction process, stripped solutions of Ni, Co, Mn, and Li raffinates were sent to precipitate the pure ternary material precursors and Li₂CO₃. This study introduces a novel method for recycling spent ternary lithium-ion batteries.

废旧三元锂离子电池（LIBs）的硫酸盐渗滤液中含有贵重金属，如过渡金属（Ni, Co, Mn）和Li，以及杂质金属，如Al和Fe。有选择地将它们从溶液中分离出来是恢复它们的必要条件。在这项工作中，提出了一种逐步溶剂萃取和沉淀工艺，用于从废旧三元锂离子电池的硫酸盐浸出液中选择性分离和回收过渡金属（Ni, Co, Mn）和Li。首先，用22.5% (v/v) N1923在磺化煤油中以1:1的O/ a比单级萃取10分钟，选择性地从溶液中去除100%的杂质金属（Al和Fe）。过渡金属（Ni, Co, Mn）和Li的损失仅为1.65%。负载有机体系中的Al和Fe用1 mol/L的HNO3溶液完全剥离，然后用碳酸钠溶液再生。随后，将萃取液（pH = 4.46）直接用于cyanex272共萃取Ni、Co和Mn。以1 mol/L Cyanex 272（皂化度50%）为有机溶剂，在磺化煤油中进行五段逆流萃取，O/A比为2.25:1。Ni、Co、Mn几乎全部被萃取，而Li仅共萃取1.43%。负载有机体系中提取的Ni、Co和Mn，以1 mol/L H2SO4和5:1的O/A比，通过五段逆流汽提完全剥离。在分步溶剂萃取过程中，将Ni、Co、Mn和Li余萃物的剥离溶液送出，沉淀出纯三元材料前驱体和Li2CO3。介绍了一种回收废旧三元锂离子电池的新方法。

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引用次数: 0