Hydrometallurgy最新文献_第3页

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 : 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

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 : 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

A novel method using CO2 to precipitate MnCO3 for a lithium-ion battery precursor 一种利用CO2沉淀锂离子电池前驱体MnCO3的新方法

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

Hydrometallurgy

Pub Date : 2025-12-07 DOI: 10.1016/j.hydromet.2025.106624

Thabo Sibanda, Senzo Mgabhi, Jemitias Chivavava, Alison E. Lewis

A novel method using carbon dioxide gas (CO₂) and ammonia (NH₃) to precipitate MnCO₃ for a lithium-ion battery precursor was investigated. This MnCO₃ was recovered from a high-tenor industrial MnSO₄ pregnant leach solution (PLS) containing Mg²⁺ and Ca²⁺ impurities. The leach solution consisted of at least 93.9 wt% Mn²⁺, 2.25 wt% Mg²⁺, and 0.14 wt% Ca²⁺. In this study, results from thermodynamic simulations were compared to experimental results. The effects of pH (5.0 to 6.6) and CO₂ bubbling time (1 to 12 h) were investigated in laboratory experiments where 0.4 L/min of CO₂ was sparged into a 1 L agitated reactor (500 rpm) containing the PLS. The thermodynamic simulation results showed that Mn²⁺ recovery is optimal in the pH range of 5.9–11.7, with recovery increasing with pH. However, high Mn²⁺ selectivity is favourable at pH < 6.6, while moderate selectivity is achieved at pH values from 6.3 to 7.2. The experimental results showed an optimal Mn recovery of 61.3 % at a pH of 6.6 and CO₂ bubbling time of 8 h. This was significantly lower than the values predicted from thermodynamic simulation (>94 % Mn recovery at pH above 5). This difference in recovery was attributed to the slow dissolution rate of CO₂. The washed MnCO₃ precipitate contained 99.0 wt% Mn, 0.13 wt% Ca, and 0.05 wt% Mg. This was equivalent to rejections of 97 % Mg²⁺ and 81 % Ca²⁺ from the MnCO₃ precipitate, respectively. The product purity met the high-purity Mn specifications but was slightly lower than the battery-grade Mn specifications (ultra-purity Mn). This study showed that carbonate precipitation using CO₂ and NH₃ can selectively recover Mn²⁺ from an industrial MnSO₄ leachate containing high Mg²⁺ and Ca²⁺ impurities, and this process has great potential for industrial application.

研究了一种利用二氧化碳气体（CO2）和氨（NH3）沉淀锂离子电池前驱体MnCO3的新方法。该MnCO3是从含有Mg2+和Ca2+杂质的高浓度工业MnSO4浸出液（PLS）中回收的。浸出液由至少93.9 wt% Mn2+， 2.25 wt% Mg2+和0.14 wt% Ca2+组成。在本研究中，热力学模拟结果与实验结果进行了比较。pH值的影响(5.0 - 6.6)和二氧化碳泡沫时间(1到12 h)在实验室实验研究,0.4 L / min的二氧化碳被喷雾成1 L搅拌反应器(500 rpm)包含请。热力学仿真结果表明Mn2 +恢复最佳pH值在5.9到-11.7之间,与复苏增加博士然而,高Mn2 +选择性有利的pH值& lt;达到6.6,而温和的选择性在pH值从6.3到7.2。实验结果表明，当pH为6.6，CO2鼓泡时间为8 h时，Mn的最佳回收率为61.3%，这明显低于热力学模拟的预测值（pH大于5时Mn的回收率为94%）。这种回收率的差异归因于CO2的溶解速度慢。洗涤后的MnCO3沉淀物含有99.0 wt% Mn， 0.13 wt% Ca和0.05 wt% Mg。这相当于从MnCO3沉淀中分别排斥97%的Mg2+和81%的Ca2+。产品纯度满足高纯Mn规格，但略低于电池级Mn规格（超纯Mn）。本研究表明，CO2和NH3碳酸盐沉淀法可以选择性地从含有高Mg2+和Ca2+杂质的工业MnSO4渗滤液中回收Mn2+，该工艺具有很大的工业应用潜力。

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引用次数: 0

Thermodynamics and kinetics of gallium extraction from a leachate of brown corundum dust 棕刚玉粉尘浸出液中镓萃取的热力学和动力学

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

Hydrometallurgy

Pub Date : 2025-12-07 DOI: 10.1016/j.hydromet.2025.106625

Cong Gao , Juhua Zhang , Xujie Hui , Wei Zhang

Brown corundum dust is a valuable gallium- containing secondary resource, with a Ga concentration ranging from 0.06 % to 0.20 %. Following alkaline leaching of brown corundum dust, a subsequent two-step carbonation-acid leaching process was implemented to reduce the levels of aluminum and silicon. However, the leachate still contained high levels of impurities, including Al, Si, K, and Fe. A solvent extraction system employing tributyl phosphate (TBP) with butyl acetate (as the diluent) was developed for the separation and purification of gallium. The mechanism by which TBP extracts gallium was elucidated by Fourier transform infrared spectroscopy, indicating an extraction reaction between the PO bond in tributyl phosphate and GaCl₄⁻. The slope analysis determined the stoichiometric ratio of these two reactants as 0.5. The thermodynamic parameters of the extraction reaction were found as ΔH^o = 40.8 kJ/mol, ΔS^o = 146 J mol⁻¹ K⁻¹, and ΔG^o = −2.58 kJ/mol. The maximum gallium loading capacity of 10 vol% TBP was determined to be 47.6 g/L. A Lewis cell was employed to investigate the influence of stirring rate, interfacial area, temperature, and reactant concentration on the kinetics of gallium extraction with TBP. The findings indicated that the extraction process was predominantly governed by the interfacial chemical reaction, exhibiting an apparent activation energy of 53.5 kJ/mol. The extraction rate equation was formulated as r₀ = 0.013[Ga]^1.21[TBP]^0.62[HCl]^0.15. In the practical solution system, the impurity elements, including Al, Si, and K, could be eliminated through solvent extraction at a rapid rate and under normal operating conditions, with the gallium extraction efficiency reaching 99.9 %.

棕刚玉粉尘是一种有价值的含镓二次资源，镓含量在0.06% ~ 0.20%之间。棕刚玉砂碱浸后，采用碳酸-酸两步浸出工艺，降低铝和硅的含量。然而，渗滤液中仍然含有大量杂质，包括铝、硅、钾和铁。以磷酸三丁酯（TBP）和乙酸丁酯为稀释剂，建立了分离纯化镓的溶剂萃取体系。傅里叶变换红外光谱分析了TBP萃取镓的机理，表明磷酸三丁酯中的PO键与GaCl4−发生了萃取反应。斜率分析确定这两种反应物的化学计量比为0.5。萃取反应的热力学参数分别为ΔHo = 40.8 kJ/mol， ΔSo = 146 J mol−1 K−1，ΔGo =−2.58 kJ/mol。测定了10 vol% TBP的最大载镓量为47.6 g/L。采用Lewis池研究了搅拌速率、界面面积、温度和反应物浓度对TBP萃取镓动力学的影响。结果表明，萃取过程主要受界面化学反应控制，表观活化能为53.5 kJ/mol。提取速率方程为r0 = 0.013[Ga]1.21[TBP]0.62[HCl]0.15。在实际溶液体系中，在正常操作条件下，通过溶剂萃取可以快速去除Al、Si、K等杂质元素，其中镓的萃取效率达到99.9%。

{"title":"Thermodynamics and kinetics of gallium extraction from a leachate of brown corundum dust","authors":"Cong Gao , Juhua Zhang , Xujie Hui , Wei Zhang","doi":"10.1016/j.hydromet.2025.106625","DOIUrl":"10.1016/j.hydromet.2025.106625","url":null,"abstract":"<div><div>Brown corundum dust is a valuable gallium- containing secondary resource, with a Ga concentration ranging from 0.06 % to 0.20 %. Following alkaline leaching of brown corundum dust, a subsequent two-step carbonation-acid leaching process was implemented to reduce the levels of aluminum and silicon. However, the leachate still contained high levels of impurities, including Al, Si, K, and Fe. A solvent extraction system employing tributyl phosphate (TBP) with butyl acetate (as the diluent) was developed for the separation and purification of gallium. The mechanism by which TBP extracts gallium was elucidated by Fourier transform infrared spectroscopy, indicating an extraction reaction between the P<img>O bond in tributyl phosphate and GaCl<sub>4</sub><sup>−</sup>. The slope analysis determined the stoichiometric ratio of these two reactants as 0.5. The thermodynamic parameters of the extraction reaction were found as Δ<em>H</em><sup>o</sup> = 40.8 kJ/mol, Δ<em>S</em><sup>o</sup> = 146 J mol<sup>−1</sup> K<sup>−1</sup>, and Δ<em>G</em><sup>o</sup> = −2.58 kJ/mol. The maximum gallium loading capacity of 10 vol% TBP was determined to be 47.6 g/L. A Lewis cell was employed to investigate the influence of stirring rate, interfacial area, temperature, and reactant concentration on the kinetics of gallium extraction with TBP. The findings indicated that the extraction process was predominantly governed by the interfacial chemical reaction, exhibiting an apparent activation energy of 53.5 kJ/mol. The extraction rate equation was formulated as <em>r</em><sub>0</sub> = 0.013[Ga]<sup>1.21</sup>[TBP]<sup>0.62</sup>[HCl]<sup>0.15</sup>. In the practical solution system, the impurity elements, including Al, Si, and K, could be eliminated through solvent extraction at a rapid rate and under normal operating conditions, with the gallium extraction efficiency reaching 99.9 %.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"240 ","pages":"Article 106625"},"PeriodicalIF":4.8,"publicationDate":"2025-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689603","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

High-purity V2O5 production from titanomagnetite leachate purified by ion exchange resin 离子交换树脂净化钛磁铁矿渗滤液制备高纯V2O5

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

Hydrometallurgy

Pub Date : 2025-12-02 DOI: 10.1016/j.hydromet.2025.106623

José Helber Vinco, Heitor Augusto Duarte, Denise Crocce Romano Espinosa, Jorge Alberto Soares Tenório

Vanadium (V), predominantly used in steel production, is also a critical element for energy storage in redox flow batteries; however, producing high-purity vanadium remains challenging. This study reports, for the first time, the use of the anion-exchange resin LSC775(SO₄) (polystyrene-based and in the sulfate form) for selective vanadium recovery from a real industrial leachate, motivated by vanadium(V) predominating as anionic vanadate species at the working pH. The feed solution originated from a secondary aqueous heap leaching, following alkaline roasting and primary leaching of vanadiferous titanomagnetite. It had a highly alkaline pH (10.3) and contained 3.7 g L⁻¹ V (∼33 %), with major contaminants Na, Si, and K (∼67 %) and minor Ca, Mg, P, Mo, Al, and Fe (∼0.2 %). Batch adsorption experiments were carried out to evaluate vanadium uptake, including equilibrium, kinetics, and thermodynamics. Fixed-bed column tests assessed vanadium breakthrough behavior, capacity, and resin reusability. Optimal V adsorption occurred at pH 2.0, consistent with the anion-exchange mechanism. The data followed the Langmuir isotherm and the pseudo-second order kinetic model, indicating monolayer adsorption via chemisorption. Thermodynamic parameters confirmed the process is endothermic (ΔH⁰ > 0) and spontaneous (ΔG⁰ < 0). In continuous-flow conditions (2 bed volumes per hour, 10 cycles), adsorption and elution efficiencies averaged 97.4 % and 98.9 %, respectively. The maximum adsorption capacity, per the Thomas model, was 249 mg g⁻¹. The resin maintained high performance over multiple cycles, confirming its stability and recyclability. Vanadium was recovered by precipitation and calcination, yielding V₂O₅ with >99.99 % purity. This work demonstrates the first successful application of LSC775(SO₄) to selective vanadium recovery from a contaminant-rich secondary leachate.

钒(V)主要用于钢铁生产，也是氧化还原液流电池中储能的关键元素；然而，生产高纯度钒仍然具有挑战性。本研究首次报道了使用阴离子交换树脂LSC775(SO4)（聚苯乙烯基和硫酸盐形式）从实际的工业渗滤液中选择性回收钒，其动力是钒(V)在工作ph值下以阴离子钒酸盐为主。原料溶液来自二次水堆浸出，经过碱性焙烧和含钒钛磁铁矿的一次浸出。它具有高碱性pH值（10.3），含有3.7 g L−1 V(~ 33%)，主要污染物Na、Si和K（~ 67%）和次要污染物Ca、Mg、P、Mo、Al和Fe（~ 0.2%）。间歇吸附实验进行了评估钒的吸收，包括平衡，动力学和热力学。固定床柱试验评估了钒的突破行为、容量和树脂的可重用性。pH为2.0时吸附V的效果最佳，符合阴离子交换机制。实验数据符合Langmuir等温线和拟二级动力学模型，表明吸附是通过化学吸附进行的单层吸附。热力学参数证实该过程为吸热（ΔH0 > 0）和自发（ΔG0 < 0）。在连续流动条件下（每小时2层体积，10个循环），吸附和洗脱效率平均分别为97.4%和98.9%。根据Thomas模型，最大吸附量为249 mg g−1。该树脂在多次循环中保持了较高的性能，证实了其稳定性和可回收性。通过沉淀和煅烧回收钒，得到纯度为99.99%的V2O5。本研究首次成功地将LSC775（SO4）应用于从富含污染物的二次渗滤液中选择性回收钒。

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引用次数: 0

Impurity incorporation and selective removal in NiSO₄•6H₂O crystals: Mechanistic insights for battery-grade purification NiSO₄•6H₂O晶体中的杂质掺入和选择性去除：电池级净化的机理见解

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

Hydrometallurgy

Pub Date : 2025-12-01 DOI: 10.1016/j.hydromet.2025.106621

Kyoung Hun Choi , Jinmyung Jang , Sevan Bedrossian , Gisele Azimi

High-purity nickel sulfate hexahydrate (NiSO₄•6H₂O) is a critical precursor for lithium-ion battery (LIB) cathode materials, particularly in the context of battery recycling and sustainable nickel supply. This study investigates the incorporation and removal behavior of key impurities, Li⁺, Na⁺, Ca²⁺, Mg²⁺, and Co²⁺, during the evaporative crystallization and purification of NiSO₄•6H₂O from synthetic solutions representative of LIB leachates. Crystals were subjected to sequential displacement and repulp washing, followed by impurity mapping through stepwise dissolution. Advanced characterization using ToF-SIMS, XRD, and SEM-EDS was employed to elucidate impurity localization and uptake mechanisms. Results reveal two distinct modes of impurity incorporation. Some impurity ions (Li⁺, Na⁺, and Ca²⁺) were predominantly surface-adsorbed and readily removed through post-crystallization washing, while Mg²⁺ and Co²⁺ were retained within the crystal lattice via isomorphous substitution with Ni²⁺. A minor fraction of Li⁺ exhibited uniform incorporation consistent with interstitial uptake. Impurity mapping confirmed solid solution behavior for Mg²⁺, Co²⁺, and residual Li⁺, while ToF-SIMS validated the surface association of Na⁺ and Li⁺. Post-crystallization purification improved nickel purity from below battery-grade to 99.87 %, highlighting the importance of tailored washing strategies. These findings provide mechanistic insight into impurity behavior in hydrated nickel sulfate systems and establish a framework for optimizing crystallization and purification to meet the stringent purity demands of battery-grade materials.

高纯度六水硫酸镍（NiSO₄•6H₂O）是锂离子电池（LIB）正极材料的关键前驱体，特别是在电池回收和可持续镍供应的背景下。研究了以LIB渗滤液为代表的合成溶液蒸发结晶纯化NiSO₄•6H₂O过程中关键杂质Li+、Na+、Ca2+、Mg2+和Co2+的掺入和去除行为。晶体经过连续的位移和再浆洗涤，然后通过逐步溶解进行杂质映射。利用ToF-SIMS、XRD和SEM-EDS进行表征，阐明了杂质的定位和吸收机制。结果显示两种不同的杂质掺入模式。一些杂质离子（Li+， Na+和Ca2+）主要被表面吸附，通过结晶后洗涤很容易去除，而Mg2+和Co2+通过Ni2+的同态取代保留在晶格内。少量Li+均匀掺入，与间隙摄取一致。杂质映射证实了Mg2+、Co2+和残余Li+的固溶体行为，而ToF-SIMS证实了Na+和Li+的表面结合。结晶后提纯将镍纯度从低于电池级提高到99.87%，突出了定制洗涤策略的重要性。这些发现为水合硫酸镍体系中的杂质行为提供了机理见解，并建立了优化结晶和纯化的框架，以满足电池级材料的严格纯度要求。

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引用次数: 0

Direct co-extraction of nickel and cobalt from sulfuric acid leachate of laterite ore using extractant DY319 in kerosene followed by impurity removal using D2EHPA to produce high purity mixed concentrated solution 用DY319萃取剂在煤油中直接共萃取红土矿硫酸浸出液中的镍和钴，再用D2EHPA除杂，制得高纯混合浓缩溶液

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

Hydrometallurgy

Pub Date : 2025-12-01 DOI: 10.1016/j.hydromet.2025.106622

Situmeang Elfrida Margaretha , Wenjing Wan , Wenjuan Guan , Mingbo Fu , Yanni An , Qinggang Li

Acid type extractants are commonly used for extracting nickel and cobalt from acid leachates of nickel laterite ore. This study aims to show the potential of the commercial acid type extractant DY319 extractant for direct co-extraction of nickel and cobalt using a synthetic sulfuric solution representing a high-pressure acid leachate of nickel laterite ore. The NMR spectroscopy characterized DY319 which has a molecular formula of C₁₆H₃₂O₂ with compound name of 4-hexyl decanoic acid. The FTIR spectroscopy of the loaded organic phase showed of the involvement of C=O group in a metal-ligand complex formation. The selectivity order of metal for DY319 followed the sequence: Cu > Zn > Ni > Co > Mn > Ca > Mg and this extractant operated better at room temperature. The McCabe-Thiele plots of the extraction at O/A phase volume ratio 1:3 with initial solution pH of 5 showed the need for 3 stages of extraction to completely separate nickel and cobalt from the solution. The stripping results indicated that nickel and cobalt can be stripped easily in low H₂SO₄ concentration with a stripping efficiency of 99.5 % for nickel and 92.4 % for cobalt. The multi-stage counter-current extraction of DY319 test was conducted and resulted in an extraction efficiency of 98.4 % Ni and 95.3 % Co. The use of D2EHPA removed impurities and resulted a final solution of 113 g/L Ni, 4.73 g/L Co, and impurities below 2 mg/L.

酸型萃取剂通常用于从红土镍矿酸浸出液中萃取镍和钴。本研究旨在展示商用酸型萃取剂DY319在红土镍矿高压酸浸出液合成硫酸溶液中直接共萃取镍和钴的潜力。负载有机相的FTIR光谱表明，C=O基团参与了金属配体配合物的形成。金属对DY319的选择性顺序为Cu >； Zn > Ni > Co > Mn > Ca > Mg，该萃取剂在室温下的萃取效果较好。在O/A相体积比为1:3、初始溶液pH为5的条件下，提取的McCabe-Thiele图显示，需要3个萃取阶段才能将镍和钴从溶液中完全分离出来。结果表明，在低H2SO4浓度条件下，镍和钴均可轻松剥离，镍和钴的剥离效率分别为99.5%和92.4%。对DY319进行了多级逆流萃取试验，镍和钴的提取率分别为98.4%和95.3%。采用D2EHPA对杂质进行了去除，最终溶液中镍和钴分别为113 g/L和4.73 g/L，杂质均低于2 mg/L。

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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 : 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

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 : 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 : 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