Hydrometallurgy最新文献_第3页

Investigating chloride sources for lithium extraction from spent lithium iron phosphate batteries using TBP: Focusing on inherent iron utilization 用TBP法研究从废磷酸铁锂电池中提取锂的氯化物来源：以固有铁的利用为重点

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

Hydrometallurgy

Pub Date : 2026-02-01 Epub Date: 2026-01-02 DOI: 10.1016/j.hydromet.2025.106628

Xitong Bi , Xiaojiao Li , Tiantian Zhao , Pengfei Ma , Mingzhang Lin , Yinxi Zhou

Solvent extraction is a critical process for lithium (Li) recovery from salt lake brine. The use of tributyl phosphate (TBP) as the extractant and ferric chloride (FeCl₃) as the co-extractant significantly enhances Li extraction efficiency and selectivity. However, this method is seldom applied for lithium recovery from spent lithium batteries (LIB). This study, proposes a novel process for recovering Li from the leachate of spent lithium iron phosphate batteries (LiFePO₄), using the iron source of LiFePO₄ to exert the effect of FeCl₃ co-extractant in the system. The system used TBP as the extractant and sulfonated kerosene as the diluent. Chlorine sources (NaCl, MgCl₂, AlCl₃) were added to investigate their effects on the extraction of Li from simulated leachate of LiFePO₄. Additionally, Li was extracted from the real leachate. Through experiments using simulated solution, it was found that the extraction efficiency of Li could reach up to 73.1 % using AlCl₃ as the external chlorine source, with a chloride ion concentration (c(Cl⁻)) of 6 mol/L, a TBP volume ratio of 70 %, an acidity of 0.025 mol/L, and an extraction time of 15 min. Under these optimal extraction conditions, the extraction efficiency of Li from the actual leachate was demonstrated to be 36.0 %, showing the feasibility of Li extraction solely by relying on iron(III) ions in the leachate. Due to the limited iron content in the leachate, the secondary extraction efficiency of Li was increased to 61.0 % by adding FeCl₃, which resulted in a final total extraction efficiency of 74.0 %.

溶剂萃取是从盐湖卤水中回收锂的关键工艺。以磷酸三丁酯（TBP）为萃取剂，氯化铁（FeCl3）为共萃取剂，显著提高了Li的萃取效率和选择性。然而，这种方法很少应用于废旧锂电池的锂回收。本研究提出了一种从废磷酸铁锂电池（LiFePO4）渗滤液中回收锂的新工艺，利用LiFePO4的铁源，在体系中发挥FeCl3共萃取剂的作用。该系统以TBP为萃取剂，磺化煤油为稀释剂。采用氯化钠（NaCl）、氯化镁（MgCl2）、氯化铝（AlCl3）等氯源对LiFePO4模拟渗滤液中锂离子的提取效果进行了研究。此外，Li是从真实的渗滤液中提取的。通过模拟溶液实验发现，以AlCl3为外氯源，氯离子浓度（c(Cl−)）为6 mol/L， TBP体积比为70%，酸度为0.025 mol/L，萃取时间为15 min时，Li的萃取效率可达73.1%。在此最佳提取条件下，实际渗滤液中锂离子的提取效率为36.0%，表明单纯依靠渗滤液中的铁离子提取锂离子是可行的。由于渗滤液中铁含量有限，加入FeCl3后，锂的二次萃取效率提高到61.0%，最终总萃取效率达到74.0%。

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引用次数: 0

Utilising micro-CT to analyse fluid dynamics in dual-porosity packing systems 利用微型ct分析双孔隙度充填系统的流体动力学

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

Hydrometallurgy

Pub Date : 2026-02-01 Epub Date: 2025-11-15 DOI: 10.1016/j.hydromet.2025.106606

Quan Zheng , Kunning Tang , Ying Da Wang , Samuel J. Jackson , Thomas Poulet , Ryan Armstrong , Peyman Mostaghimi

This paper introduces a workflow for creating and analysing an engineered dual-porosity system, similar to those in copper heap leaching, by synthesising micro-porous chalcopyrite-glass beads. These beads are designed to match the size and shape of single-porosity glass beads. X-ray micro-CT imaging is utilised alongside mass balance measurements on comparative irrigation experiments in the dual and single-porosity systems to investigate the complex fluid dynamics governing the interaction between fluid flow in the micro-porous (intraparticle) and macroscopic (interparticle) domains. Results demonstrate that the dual porosity system, with 20% micro-porosity and 46% macro-porosity, retains over twice the liquid volume compared to the single porosity system, with the same macro-porosity and tortuosity. An increased macroscopic flow connectivity and liquid content is observed in the dual porosity system, due to lateral flow within the micro-pores that enhance surface area and connectivity at the bead contact points. A considerable amount of liquid is retained in the micro-pores through capillary forces, which impacts leaching performance in a large scale system. Overall, this imaging-based methodology and workflow provides a robust framework for designing and analysing engineered dual-porosity systems found in geosciences, chemical engineering, and hydrometallurgy, enabling improved prediction and optimisation of reactive transport and resource recovery processes in complex porous media.

本文介绍了通过合成微孔黄铜矿-玻璃微珠，建立和分析一个类似于铜堆浸的工程双孔系统的工作流程。这些珠子的设计与单孔玻璃珠子的大小和形状相匹配。x射线微ct成像与质量平衡测量一起用于双孔和单孔系统的比较灌溉实验，以研究控制微孔（颗粒内）和宏观（颗粒间）流体流动之间相互作用的复杂流体动力学。结果表明，在宏观孔隙度和弯曲度相同的情况下，微孔隙度为20%、宏观孔隙度为46%的双孔隙度体系比单一孔隙度体系保留了两倍以上的液体体积。在双孔隙系统中，由于微孔内的横向流动增加了表面面积和珠状接触点的连通性，可见宏观流动连通性和液体含量增加。大量的液体通过毛细力滞留在微孔中，影响了大规模系统的浸出性能。总的来说，这种基于成像的方法和工作流程为设计和分析在地球科学、化学工程和湿法冶金中发现的工程双孔隙系统提供了一个强大的框架，能够改进复杂多孔介质中反应输运和资源回收过程的预测和优化。

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引用次数: 0

The use of ultrasound technology for the inhibition of mineral scale formation in mixing tanks 利用超声波技术抑制混合槽中矿物结垢的形成

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

Hydrometallurgy

Pub Date : 2026-02-01 Epub Date: 2025-11-28 DOI: 10.1016/j.hydromet.2025.106619

Joydip Mondal, Shen Long, Jie Wu

Gypsum scale formation is a major challenge in many unit operations within the minerals processing industry. Conventional techniques for removing such scales in mixing tanks are time-consuming, labour-intensive and potentially hazardous, highlighting the need for new inhibition strategies. An experimental study on the effect of ultrasound in inhibiting gypsum scale in mixing tanks at laboratory scale was conducted. A 2 L cylindrical tank, employing an unbaffled agitator system and ultrasonic transducer, was used to test the effect of varying sonication times (1 to 6 h per day), and power levels (3 to 4.25 W). Scale-mitigation parameters based on the area fraction of descaled surface, the total scale mass and scale thickness were proposed and assessed. Results revealed that intermittent application of ultrasound significantly reduces gypsum scale deposition, while the scale inhibition improved with an increase in sonication time and power. The most effective setup was found to be 6 h/day of ultrasound at 4.25 W, which achieved almost 97 % reduction in scale mass and thickness at the end of five days of scaling compared to cases without ultrasound. Acoustic analysis indicated that ultrasonic waves with multiple frequencies between 20 and 400 kHz, alongside cavitation and streaming flows, help inhibit scale formation on the tank surfaces.

石膏结垢的形成是矿物加工业中许多单元操作的主要挑战。在混合罐中清除此类水垢的传统技术耗时、劳动密集且存在潜在危险，因此需要新的抑制策略。在实验室规模下，对超声抑制混合槽中石膏结垢的效果进行了实验研究。使用一个2l圆柱形槽，采用无挡板搅拌系统和超声波换能器，测试不同超声时间（每天1至6小时）和功率水平（3至4.25 W）的效果。提出并评价了基于去鳞面面积分数、总鳞质量和鳞厚的减垢参数。结果表明，超声间歇应用可显著降低石膏水垢沉积，且随着超声时间和功率的增加，水垢抑制作用增强。最有效的设置是在4.25 W下进行6小时/天的超声治疗，与没有超声的病例相比，在5天的结垢结束时，结垢质量和厚度减少了近97%。声学分析表明，频率在20 ~ 400 kHz之间的超声波，以及空化和流动，有助于抑制罐表面的结垢。

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引用次数: 0

Reductive Bayer digestion of high‑titanium bauxite followed by sulfuric acid leach-roast-leach-hydrolyze process to recover H2TiO3 and TiO2 高钛铝土矿拜耳还原溶出-硫酸浸出-焙烧浸出-水解工艺回收H2TiO3和TiO2

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

Hydrometallurgy

Pub Date : 2026-02-01 Epub Date: 2026-01-12 DOI: 10.1016/j.hydromet.2026.106631

Yuguan Zhang , Yilin Wang , Tiangui Qi , Qiusheng Zhou , Zhihong Peng , Guihua Liu , Xiaobin Li

Bauxite residue is the solid waste produced during alumina refining process. The economic utilization of the titanium minerals present in the waste can both significantly lower alumina production costs and considerably reduce the overall volume of bauxite residue. This paper presents an innovative method that combines: (i) reductive Bayer digestion with sulfuric acid roasting, (ii) stepwise enrichment and effective extraction of titanium dioxide from bauxite residue. Compared to the Bayer digestion with the addition of lime, reductive Bayer process significantly enriched the titanium dioxide content in bauxite residue from 13.9% to 20.1%. Subsequent acid leaching can enhance the concentration of titanium dioxide to 38.3%, while the control group, affected by the formation of calcium sulfate, reaches only 13.7%. Significant enrichment of rare earth elements was observed in the acid-leached product, with Sc₂O₃ concentration attaining 248 g/t as a representative. Titanium-rich material can be directly transformed into high-purity meta-titanic acid products using a sulfuric acid roasting-hydrolysis method, which achieves a purity level of 93.4% after the roasting process. This technology lays a significant foundation for the value-added utilization of high‑titanium bauxite and the substantial reduction of bauxite residue discharges.

铝土矿渣是氧化铝精炼过程中产生的固体废物。废渣中钛矿物的经济利用既可以显著降低氧化铝生产成本，又可以显著减少铝土矿渣的总体积。本文提出了一种将还原拜耳消解与硫酸焙烧相结合的创新方法，以及从铝土矿渣中逐步富集和有效提取二氧化钛的方法。与添加石灰的拜耳消化法相比，还原性拜耳消化法显著提高了铝土矿渣中二氧化钛的含量，由13.9%提高到20.1%。后续酸浸可将钛白粉浓度提高至38.3%，而对照组受硫酸钙形成的影响，钛白粉浓度仅为13.7%。酸浸产物中稀土元素显著富集，以Sc2O3浓度达到248 g/t为代表。采用硫酸焙烧-水解法可将富钛材料直接转化为高纯度的元钛酸产品，焙烧工艺后纯度可达93.4%。该技术为高钛铝土矿的增值利用和大量减少铝土矿渣排放奠定了重要基础。

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引用次数: 0

Enhancement of selective lithium extraction from α-spodumene by autoclaving with NaOH and NaAlO2 at 200–300 °C NaOH和NaAlO2在200-300℃高压灭菌强化α-锂辉石中锂的选择性萃取

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

Hydrometallurgy

Pub Date : 2026-02-01 Epub Date: 2025-12-13 DOI: 10.1016/j.hydromet.2025.106626

Shuhao Dong , Yakai Yang , Hao Zhang , Meiyan Yu , Hui Guo , Ge Kuang , Haidong Wang , Xiaohui Fan

Spodumene is an important lithium-bearing mineral which naturally exists as chemically inert α phase. Therefore, a calcination process at 1100 °C is traditionally employed for phase transformation to β phase, causing a large energy consumption. This work proposes an improved alkaline autoclave method using NaOH and NaAlO₂ aiming to extract lithium directly from α-spodumene. Interestingly, the addition of NaAlO₂ can significantly enhance the lithium extraction efficiency from 50.5 % (dissolution with NaOH only) to 94.7 %. Moreover, the investigation of dissolution behavior indicated that the added AlO₂⁻ can capture the dissolved Si, releasing more lithium into lixivium and achieving an efficient separation of Li from Si. The lithium-containing leachate was then directly evaporated to concentrate and prepare Li₂CO₃. Besides, the efficiency of lithium extraction still can remain at a relatively high level around 90 % with three cyclic dissolution steps by recycled alkaline liquor. This combined autoclave method shows potential as a promising way to extract lithium directly from α-spodumene without phase transformation at high temperature.

锂辉石是一种重要的含锂矿物，天然存在于化学惰性的α相中。因此，传统上采用1100℃的煅烧工艺将其转化为β相，能耗较大。本研究提出了一种改进的碱蒸法，利用NaOH和NaAlO2直接从α-锂辉石中提取锂。有趣的是，NaAlO2的加入可以显著提高锂的萃取效率，从50.5%（仅用NaOH溶解）提高到94.7%。此外，对溶解行为的研究表明，添加的AlO2−可以捕获溶解的Si，将更多的锂释放到浸出液中，实现了Li和Si的有效分离。然后将含锂渗滤液直接蒸发浓缩制备Li2CO3。此外，利用循环碱液进行三步溶出，锂的萃取效率仍可保持在90%左右的较高水平。该方法是一种在高温下直接从α-锂辉石中提取锂而不发生相变的有效方法。

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引用次数: 0

Integrated acid leaching of spent battery cathode material (LCO, NMC111) and flotation tailings of pyrite and pyrrhotite 废电池正极材料（LCO、NMC111）与黄铁矿、磁黄铁矿浮选尾矿的综合酸浸

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

Hydrometallurgy

Pub Date : 2026-02-01 Epub Date: 2025-11-22 DOI: 10.1016/j.hydromet.2025.106618

Anssi Karppinen, Henna Liljanko, Sipi Seisko, Mari Lundström

Lithium-ion batteries require number of metals which have been listed as critical raw materials in European Union due to their supply risk and economic importance. Therefore, more emphasis needs to be put on (i) recycling of spent batteries, (ii) utilizing other secondary sources of battery metals and primary mining waste. In this research, leaching of battery metals from cathode materials—lithium cobalt oxide (LCO) and lithium nickel manganese cobalt oxide (NMC111)—was investigated with the aim to use waste fraction of primary mining, namely sulfide-rich flotation tailings, as reductant. Two types of tailings were investigated in the current study: pyrrhotite-pyrite tailings and pyrite tailings. These tailings contain reductive power necessary for leaching, as well as battery metals incorporated in the sulfide matrix. The investigated parameters were temperature (40–80 °C) and mass ratio of cathode material and tailings (0.5–2 g/g) whereas S/L-ratio (100 g/L), acid concentration ([H₂SO₄] = 1 M), and leaching time (180 min) were kept constant. The results showed that both pyrrhotite-pyrite as well as pyrite dominated tailings can act as an effective reductant for the leaching of metals from cathode materials. The extraction efficiency of battery metals correlate with dissolved iron concentration. When only pyrite tailings were used in the process, the reductive effect of S₂²⁻ could also be recognized as lower concentration of dissolved Fe²⁺ was required when compared to use of pyrrhotite tailings. At 80 °C, LCO and NMC could be completely dissolved within 60min while simultaneous extraction of battery metals from sulfide flotation tailings was up to 17 % of Ni, 15 % of Co, and 27 % of Cu.

锂离子电池需要一些金属，由于其供应风险和经济重要性，这些金属已被列为欧盟的关键原材料。因此，需要更加强调(i)回收废旧电池，（ii）利用电池金属和初级采矿废物的其他次级来源。本研究以一次采矿废段即富硫化物浮选尾矿为还原剂，对正极材料锂钴氧化物（LCO）和锂镍锰钴氧化物（NMC111）中电池金属的浸出进行了研究。本研究研究了两类尾矿：磁黄铁矿尾矿和黄铁矿尾矿。这些尾矿含有浸出所需的还原力，以及硫化物基质中含有的电池金属。研究温度（40 ~ 80℃）、正极料与尾矿质量比（0.5 ~ 2 g/g）为恒定参数，S/L比（100 g/L）、酸浓度（[H2SO4] = 1 M）、浸出时间（180 min）为恒定参数。结果表明，磁黄铁矿和以黄铁矿为主的尾矿均可作为阴极材料中金属浸出的有效还原剂。电池金属的萃取效率与溶铁浓度有关。当只使用黄铁矿尾矿时，S22−的还原效果也可以被认可，因为与使用磁黄铁矿尾矿相比，S22−所需的溶解Fe2+浓度更低。在80℃条件下，LCO和NMC可在60min内完全溶解，同时从硫化浮选尾矿中提取电池金属，镍含量可达17%，Co含量为15%，Cu含量为27%。

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引用次数: 0

Studtite dissolution in the presence of organic complexants relevant to nuclear waste disposal 研究与核废料处理有关的有机络合物存在下的溶解

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

Hydrometallurgy

Pub Date : 2026-02-01 Epub Date: 2025-11-20 DOI: 10.1016/j.hydromet.2025.106610

Zachary Murphy , Rachel Cohen , David Rai II , Cassandra Munoz , Caleb Johnson , Edwin Davidson , Swadeshmukul Santra , Vasileios Anagnostopoulos

Studtite (UO₂O₂∙4H₂O), a uranyl peroxide mineral, has been found in nuclear waste storage tanks alongside complexing agents such as EDTA, HEDTA, and NTA. The influence of these ligands on the fate and transport of uranium, a risk driving contaminant, is critical for understanding the consequences of nuclear waste leakages. This study investigated the stability of studtite in the presence of these ligands under varying pH conditions (3, 7, 9, and 11), ligand concentrations (0.15 mM, 1.5 mM, and 15 mM), and ionic strengths. Batch kinetic experiments were conducted with 1 mg of studtite in 50 mL suspensions (12.7 mg/L total U), and the uranium concentration in the aqueous phase was monitored over time. Results showed uranium release from studtite even in the absence of ligands at pH 3 and 11, while at pH 7 and 9 uranium was only released in the presence of ligands. The presence of EDTA and NTA increased aqueous uranium at pH 7 and 9 by forming soluble U-ligand complexes, as confirmed by NMR and speciation diagrams. HEDTA enhanced studtite dissolution at all tested pH values. Increased ionic strength reduced electrostatic repulsion between ligands and the mineral surface, further promoting dissolution. In simulated nuclear waste, uranium predominantly favored the aqueous phase regardless of ligand presence. These findings indicate that EDTA, HEDTA or NTA presence in waste can provide a pathway for studtite dissolution, increasing the amount of aqueous uranium in waste while also changing aqueous uranium speciation. This impacts the mobility of contaminated waste in the occurrence of waste leakage, complicating uranium fate and transport in the environment. These findings have implications for uranium fate and transport modeling and the development of nuclear waste treatment strategies.

studite （UO2O2∙4H2O）是一种铀酰过氧化物矿物，在核废料储存罐中与EDTA、HEDTA和NTA等络合剂一起被发现。这些配体对铀这种危险驱动污染物的命运和运输的影响，对于了解核废料泄漏的后果至关重要。本研究考察了这些配体在不同pH条件（3、7、9和11）、配体浓度（0.15 mM、1.5 mM和15 mM）和离子强度下的稳定性。在50 mL （12.7 mg/L总U）的悬浮液中加入1mg studtite，进行间歇动力学实验，并随时间监测水相中的铀浓度。结果表明，在pH为3和11时，铀在没有配体的情况下也有释放，而在pH为7和9时，铀只有在有配体的情况下才有释放。EDTA和NTA的存在通过形成可溶的u配体复合物增加了pH值为7和9的水中铀，核磁共振和形态图证实了这一点。在所有测试的pH值下，HEDTA增强了研究品的溶解。离子强度的增加减少了配体和矿物表面之间的静电斥力，进一步促进了溶解。在模拟核废料中，不管配体是否存在，铀主要倾向于水相。这些发现表明，EDTA、HEDTA或NTA在废物中的存在可以为研究中的溶解提供途径，增加废物中水中铀的量，同时也改变水中铀的形态。这影响了受污染废物的流动性，发生废物泄漏，使铀在环境中的命运和运输复杂化。这些发现对铀的命运和运输模型以及核废料处理策略的发展具有重要意义。

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引用次数: 0

A clean and efficient technology for lithium, rubidium, and cesium recovery from lepidolite using alkaline pressure leaching and alkaline solvent extraction with LIX 54 and TRPO 用lix54和TRPO进行碱性压力浸出和碱性溶剂萃取从锂云母中回收锂、铷和铯的清洁高效工艺

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

Hydrometallurgy

Pub Date : 2026-02-01 Epub Date: 2025-12-24 DOI: 10.1016/j.hydromet.2025.106620

Xiaozhou Zhou , Tong Zhong , Wenjuan Guan , Mingyu Wang , Shengxi Wu , Xinsheng Wu , Zuoying Cao , Qinggang Li , Guiqing Zhang

Lepidolite is one of the important resources containing Li, Rb, and Cs. Currently, sulfate roasting is the predominant industrial method for processing lepidolite. However, this approach faces challenges including low comprehensive recovery, high energy consumption, and significant reagent usage. This study introduces a clean and efficient technology for recovering Li, Rb, and Cs from lepidolite, based on alkali and water cycles. The process encompasses collaborative leaching with a mixture of sodium hydroxide (NaOH) and calcium hydroxide (Ca(OH)₂), selective impurity removal using Ca(OH)₂, and alkaline extraction for lithium recovery. Experimental results demonstrated that the leachate could be recycled 2 times to enrich Li, Rb, and Cs. The average leaching efficiencies after 2 cycles were: 92.7 % Li, 94.3 % Rb, 94.5 % Cs, and 94.6 % K, under the leaching conditions of 400 g/L NaOH, 0.6 of mass ratio of Ca(OH)₂/ore, <106 μm particle size, 5 h reaction time and 250 °C. The XRD and SEM-EDS analyses revealed that the leach residue comprised the phases Ca_0.63Fe_2.37Fe₂(SiO₄)₃, NaCaHSiO₄, CaF₂, and Fe₃O₄. Furthermore, Ca(OH)₂ was employed for selective impurity removal from the solution, achieving a valuable metal loss of only 0.67 %. Subsequently, Li was efficiently recovered via synergistic solvent extraction using dodecyl phenyl methyl-β-diketone (LIX 54) and trialkylphosphine oxide (TRPO). The 85 % volume fractions of raffinate of Li could be returned to pressure leaching to reuse H₂O and NaOH. The process developed in this study features environmental friendliness, high comprehensive recovery, and low reagent consumption, providing a promising approach for the clean and efficient utilization of lepidolite.

锂云母是含Li、Rb、Cs的重要资源之一。目前，硫酸盐焙烧是加工锂云石的主要工业方法。然而，这种方法面临着综合回收率低、能耗高、试剂使用量大等挑战。介绍了一种基于碱循环和水循环的锂云母中Li、Rb、Cs的清洁高效回收工艺。该工艺包括氢氧化钠（NaOH）和氢氧化钙（Ca(OH)2）的混合物协同浸出，使用Ca(OH)2选择性去除杂质，以及碱性提取锂回收。实验结果表明，该渗滤液可循环利用2次，富集Li、Rb和Cs。在NaOH浓度为400 g/L、Ca(OH)2/ore质量比为0.6、粒径为106 μm、反应时间为5 h、温度为250℃的条件下，2个循环后的平均浸出效率分别为：Li 92.7%、Rb 94.3%、Cs 94.5%、K 94.6%。XRD和SEM-EDS分析表明，浸出渣由Ca0.63Fe2.37Fe2(SiO4)3、NaCaHSiO4、CaF2和Fe3O4相组成。此外，Ca(OH) 2用于选择性去除溶液中的杂质，使有价金属损失率仅为0.67%。随后，采用十二烷基苯基甲基-β-二酮（LIX 54）和氧化三烷基膦（TRPO）协同溶剂萃取，高效回收Li。85%体积分数的锂精矿可返回压力浸出，以重复利用H2O和NaOH。本研究开发的工艺具有环境友好、综合回收率高、试剂消耗少等特点，为锂云石的清洁高效利用提供了一条有前景的途径。

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引用次数: 0

Solvent extraction using crown ethers: Selective recovery of potassium from synthetic K-feldspar leachate 冠醚溶剂萃取：从合成钾长石渗滤液中选择性回收钾

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

Hydrometallurgy

Pub Date : 2026-01-01 Epub Date: 2025-10-17 DOI: 10.1016/j.hydromet.2025.106597

Sina Shakibania, Lena Sundqvist-Öqvist, Sepideh Javanshir, Jan Rosenkranz

The present study focuses on the selective extraction of potassium from a hydrochloric acid-based feldspar leachate using solvent extraction with crown ethers, CE (dibenzo-18-crown-6 and 12-crown-4). The effects of hydrochloric acid concentration, extractant type, diluent, extractant concentration, and organic-to-aqueous phase ratio on potassium extraction efficiency have been examined. Dibenzo-18-crown-6 diluted in m-cresol was shown to preferentially extract potassium (≈85 %) from highly acidic hydrochloric acid solutions (2 to 6 M), with minimal co-extraction of impurities, such as aluminum and sodium, in a single extraction step. Aluminum, however, was shown to be extracted efficiently (≈99 %) at lower acidities (<0.1 M). The extraction mechanisms were explored using various analyses, such as slope analysis, nuclear magnetic resonance, and scanning electron microscopy showing that dibenzo-18-crown-6 forms a highly stable complex with potassium at 1:1 M ratio, (KCl)(CE), driven by the size compatibility between potassium ions and the crown ether cavity. For aluminum, the extraction mechanism likely involves the formation of a cooperative complex where aluminum ions are associated with the potassium-crown ether complex (AlKCl₄)(CE). Increasing the concentration of hydrochloric acid increased potassium ion activity, chloride ion activity, and ionic strength in the solution. These changes would enhance selective potassium extraction over the formation and extraction of the aluminum‑potassium cooperative complex.

研究了冠醚、CE（二苯并-18-冠-6和12-冠-4）溶剂萃取法从盐酸长石渗滤液中选择性提取钾。考察了盐酸浓度、萃取剂类型、稀释剂、萃取剂浓度、有机水相比等因素对钾萃取效率的影响。在间甲酚中稀释的二苯并-18-冠-6在高酸性盐酸溶液（2 ~ 6 M）中优先提取钾（≈85%），在单个提取步骤中，杂质（如铝和钠）的共提取量最小。然而，在较低的酸度（<0.1 M）下，铝被有效地提取（≈99%）。利用斜率分析、核磁共振和扫描电镜等方法对萃取机理进行了探讨，结果表明，在钾离子与冠醚腔的尺寸相容性驱动下，二苯并-18-冠-6与钾离子以1:1的M比（KCl）（CE）形成了高度稳定的配合物。对于铝，萃取机制可能涉及到一个配合物的形成，其中铝离子与钾冠醚配合物（AlKCl4）（CE）相结合。盐酸浓度的增加使溶液中的钾离子活性、氯离子活性和离子强度增加。这些变化将增强选择性钾的提取，而不是铝钾配合物的形成和提取。

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引用次数: 0

Enhancing selective extraction and recovery of critical metals from spent NCM black mass through a leaching procedure followed by precipitation and liquid-liquid extraction processes 通过浸出程序，然后是沉淀和液-液萃取过程，加强从废NCM黑色物质中选择性提取和回收关键金属

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

Hydrometallurgy

Pub Date : 2026-01-01 Epub Date: 2025-11-14 DOI: 10.1016/j.hydromet.2025.106604

Nityanand Singh , Kedhareswara Sairam Pasupuleti , Hee-Nam Kang , Tae-Hyuk Lee , Jin-Young Lee

The management of spent Nickel-Cobalt-Manganese (NCM) type lithium-ion batteries (LIBs) is critical to advancing sustainable development and aligning with circular economy principles. This study proposes an efficient hydrometallurgical process for the recovery of valuable metals from LiNi_xCo_yMn_zO₂ black mass powder. The leaching process was optimized under specific conditions, namely a 1 M H₂SO₄ concentration, 15 % (v/v) H₂O₂, and a liquid-to-solid ratio of 100 g/L at 75 °C, with a mixing time of 120 min. These parameters facilitated the leaching of more than 95 % of Cu(II), Ni(II), Co(II), Mn(II), and Li(I). Subsequent metal recovery processes were conducted under carefully controlled conditions. Copper (Cu(II)) was extracted using 20 % (v/v) LIX 84-I at a pH of 2.7. Manganese (Mn(II)) was precipitated using KMnO₄ at a pH of 2.0. Cobalt (Co(II)) was extracted with Ionquest 290 at pH 4.5, followed by stripping with 10 % (v/v) H₂SO₄ and crystallization to produce CoSO₄.H₂O crystals. Nickel (Ni(II)) was recovered as nickel sulfide at pH 3, while lithium (Li(I)) was concentrated through evaporation and subsequently precipitated with sodium carbonate (Na₂CO₃) at pH 12, under conditions of 85 °C and 35 min of stirring. The findings contribute to the development of more sustainable processes for the recycling of spent LIBs, emphasizing the importance of optimizing extraction and precipitation techniques to maximize resource recovery and minimize environmental impact.

废旧镍钴锰（NCM）型锂离子电池（LIBs）的管理对于推进可持续发展和符合循环经济原则至关重要。本研究提出了一种从LiNixCoyMnzO2黑色块状粉末中回收有价金属的高效湿法冶金工艺。在特定条件下，即H2SO4浓度为1 M， H2O2浓度为15% (v/v)，液固比为100 g/L，温度为75℃，混合时间为120 min，对浸出过程进行了优化。这些参数有利于95%以上的Cu（II）、Ni（II）、Co（II）、Mn（II）和Li(I)的浸出。随后的金属回收过程在严格控制的条件下进行。用20% (v/v) LIX 84-I萃取铜（Cu(II)）， pH为2.7。用KMnO4在pH为2.0的条件下沉淀锰（Mn(II)）。在pH 4.5条件下，用Ionquest 290萃取钴（Co(II)），用10% (v/v) H2SO4溶出，结晶生成CoSO4。H2O晶体。镍（Ni(II)）在pH为3的条件下被回收为硫化镍，锂（Li(I)）通过蒸发浓缩，随后在pH为12的条件下与碳酸钠（Na2CO3）在85℃和搅拌35 min的条件下沉淀。研究结果有助于开发更可持续的废lib回收过程，强调了优化提取和沉淀技术以最大化资源回收和最小化环境影响的重要性。

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