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Understanding the effect of roasting on vanadium speciation in steel slags and impact on leaching
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2025-02-01 DOI: 10.1016/j.hydromet.2024.106433
Shailendra K. Sharma , Megan L. Girdwood , Tanzeel Arif , Aston C. Pearcy , Campbell M. Tiffin , Aaron T. Marshall , Chris W. Bumby
Vanadium is an extremely useful element that is primarily sourced from steelmaking slags via hydrometallurgical processes that use an oxidative roasting step. This roasting step oxidises vanadium to soluble high valent states and influences vanadium extraction in the subsequent leach step. This study examines the structural and speciation behaviour of vanadium in vanadium-rich slag during roasting and investigate how it affects the extraction efficiency of vanadium during leaching. Vanadium-rich slag was roasted at a range of temperatures under air or argon, and was characterized via standard techniques: XRD, SEM/EDS and XAS. XRD and SEM/EDS analyses showed that increasing roasting temperature or time resulted in greater destruction of vanadium spinel, with the released vanadium migrating with manganese to form a vanadium‑manganese rich phase. X-ray absorption spectroscopy showed a clear increase in the presence of V(V) with increasing roasting temperature. Leaching these roasted slags with a mildly acidic sodium acetate buffer solution (pH = 4) gave greater vanadium extraction efficiencies for slag samples that had higher proportions of V(V). This work thoroughly describes the changes in structure and speciation that occur in vanadium-rich slag during the roasting step, and shows the impact that roasting has upon extraction efficiencies in the following leaching step, justified by testing the elemental accountability.
{"title":"Understanding the effect of roasting on vanadium speciation in steel slags and impact on leaching","authors":"Shailendra K. Sharma ,&nbsp;Megan L. Girdwood ,&nbsp;Tanzeel Arif ,&nbsp;Aston C. Pearcy ,&nbsp;Campbell M. Tiffin ,&nbsp;Aaron T. Marshall ,&nbsp;Chris W. Bumby","doi":"10.1016/j.hydromet.2024.106433","DOIUrl":"10.1016/j.hydromet.2024.106433","url":null,"abstract":"<div><div>Vanadium is an extremely useful element that is primarily sourced from steelmaking slags <em>via</em> hydrometallurgical processes that use an oxidative roasting step. This roasting step oxidises vanadium to soluble high valent states and influences vanadium extraction in the subsequent leach step. This study examines the structural and speciation behaviour of vanadium in vanadium-rich slag during roasting and investigate how it affects the extraction efficiency of vanadium during leaching. Vanadium-rich slag was roasted at a range of temperatures under air or argon, and was characterized <em>via</em> standard techniques: XRD, SEM/EDS and XAS. XRD and SEM/EDS analyses showed that increasing roasting temperature or time resulted in greater destruction of vanadium spinel, with the released vanadium migrating with manganese to form a vanadium‑manganese rich phase. X-ray absorption spectroscopy showed a clear increase in the presence of V(V) with increasing roasting temperature. Leaching these roasted slags with a mildly acidic sodium acetate buffer solution (pH = 4) gave greater vanadium extraction efficiencies for slag samples that had higher proportions of V(V). This work thoroughly describes the changes in structure and speciation that occur in vanadium-rich slag during the roasting step, and shows the impact that roasting has upon extraction efficiencies in the following leaching step, justified by testing the elemental accountability.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"232 ","pages":"Article 106433"},"PeriodicalIF":4.8,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143157110","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Laterite ore processing with hydrogen via mild chemical pressure leaching or bioleaching
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2025-02-01 DOI: 10.1016/j.hydromet.2025.106447
Axel Schippers, Stefanie A. Hetz, Christian Ostertag-Henning
Limonitic laterites consist of a high amount of iron oxides/hydroxides, such as goethite and hematite, being recalcitrant in hydrometallurgical processing for nickel and cobalt recovery. High pressure acid leaching (HPAL) is the currently most applied processing technology for limonitic laterites. Still, research is ongoing to develop technologies with less energy consumption and a lower carbon footprint. Among these, chemical leaching under mild conditions and bioleaching were investigated, as well as using hydrogen gas as a reductant. In this study, these approaches were combined. Bioleaching of laterite ore using hydrogen was shown for the first time, and anaerobic batch incubation with Acidithiobacillus ferrooxidans showed that bioleaching with hydrogen was as efficient in metal extraction as with addition of elemental sulfur. Chemical laterite leaching with hydrogen under pressure at 50 bar and ambient temperature also succeeded in metal extraction; however, the leaching efficiency strongly depended on the laterite mineralogical composition.
{"title":"Laterite ore processing with hydrogen via mild chemical pressure leaching or bioleaching","authors":"Axel Schippers,&nbsp;Stefanie A. Hetz,&nbsp;Christian Ostertag-Henning","doi":"10.1016/j.hydromet.2025.106447","DOIUrl":"10.1016/j.hydromet.2025.106447","url":null,"abstract":"<div><div>Limonitic laterites consist of a high amount of iron oxides/hydroxides, such as goethite and hematite, being recalcitrant in hydrometallurgical processing for nickel and cobalt recovery. High pressure acid leaching (HPAL) is the currently most applied processing technology for limonitic laterites. Still, research is ongoing to develop technologies with less energy consumption and a lower carbon footprint. Among these, chemical leaching under mild conditions and bioleaching were investigated, as well as using hydrogen gas as a reductant. In this study, these approaches were combined. Bioleaching of laterite ore using hydrogen was shown for the first time, and anaerobic batch incubation with <em>Acidithiobacillus ferrooxidans</em> showed that bioleaching with hydrogen was as efficient in metal extraction as with addition of elemental sulfur. Chemical laterite leaching with hydrogen under pressure at 50 bar and ambient temperature also succeeded in metal extraction; however, the leaching efficiency strongly depended on the laterite mineralogical composition.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"233 ","pages":"Article 106447"},"PeriodicalIF":4.8,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143212494","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Research on the short-process of leaching and semi-extraction method of nickel‑cobalt from mixed hydroxide precipitate (MHP) to prepare battery grade products
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2025-01-29 DOI: 10.1016/j.hydromet.2025.106446
Yukun Shen , Hongyu Wang , Liang Zhang , Liyong Zhou , Chunping Fu , Kweon Ho Jin , Mingkang Fang , Jiade Wang
Mixed nickel‑cobalt hydroxide precipitate (MHP) obtained via pretreatment and leaching of nickel laterite ore, is a vital source of nickel and cobalt. This work proposes an efficient and economical hydrometallurgical process for recovering Ni and Co from MHP. Initially, an acid leaching process was employed, achieving leaching efficiencies of 99.9 % for Ni and 98.3 % for Co. Notably, the leaching efficiency for Mn was significantly lower at 26.1 %, attributed to partial oxidation of Mn. Subsequently, the purification of the leach liquor resulted in a significant reduction of impurities such as Si, Sc, Fe, and Al to concentrations of 18 mg/L, 1.8 mg/L, 0.8 mg/L, and 0.8 mg/L, respectively. Finally, the subsequent semi-extraction process further minimized impurities, including Co, Mn, Mg, and Ca, to levels below 1 mg/L in the purified solution. Furthermore, the Sc enriched in P204 was stripped by 3 mol/L NaOH, yielding a Sc-enriched solid residue with a grade of 30 %. The results show that the process can extract Ni and Co from MHP, and Ni, Co solution are suitable for the production of lithium batteries.
{"title":"Research on the short-process of leaching and semi-extraction method of nickel‑cobalt from mixed hydroxide precipitate (MHP) to prepare battery grade products","authors":"Yukun Shen ,&nbsp;Hongyu Wang ,&nbsp;Liang Zhang ,&nbsp;Liyong Zhou ,&nbsp;Chunping Fu ,&nbsp;Kweon Ho Jin ,&nbsp;Mingkang Fang ,&nbsp;Jiade Wang","doi":"10.1016/j.hydromet.2025.106446","DOIUrl":"10.1016/j.hydromet.2025.106446","url":null,"abstract":"<div><div>Mixed nickel‑cobalt hydroxide precipitate (MHP) obtained via pretreatment and leaching of nickel laterite ore, is a vital source of nickel and cobalt. This work proposes an efficient and economical hydrometallurgical process for recovering Ni and Co from MHP. Initially, an acid leaching process was employed, achieving leaching efficiencies of 99.9 % for Ni and 98.3 % for Co. Notably, the leaching efficiency for Mn was significantly lower at 26.1 %, attributed to partial oxidation of Mn. Subsequently, the purification of the leach liquor resulted in a significant reduction of impurities such as Si, Sc, Fe, and Al to concentrations of 18 mg/L, 1.8 mg/L, 0.8 mg/L, and 0.8 mg/L, respectively. Finally, the subsequent semi-extraction process further minimized impurities, including Co, Mn, Mg, and Ca, to levels below 1 mg/L in the purified solution. Furthermore, the Sc enriched in P204 was stripped by 3 mol/L NaOH, yielding a Sc-enriched solid residue with a grade of 30 %. The results show that the process can extract Ni and Co from MHP, and Ni, Co solution are suitable for the production of lithium batteries.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"233 ","pages":"Article 106446"},"PeriodicalIF":4.8,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143379166","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
Investigation of hydrodynamics behavior in a gas-agitated disc and doughnut column for solvent extraction with application to impurity removal from mixed nickel‑cobalt hydroxide precipitate
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2025-01-27 DOI: 10.1016/j.hydromet.2025.106438
Chi Wang , Dongbing Xu , Boren Tan , Chao Chang , Chenye Wang , Yong Wang , Peng Xing , Huiquan Li , Xiahui Gui , Jianguo Yang
Controlling the dispersed phase droplet size within a reasonable range in the extraction column is crucial for enhancing mass transfer efficiency. Traditional high energy-inputs may result in excessive droplet fragmentation in low interfacial tension systems, posing significant challenges in intensifying the extraction process. This work proposes a novel gas-agitated technology to prevent excessive droplet fragmentation. Three extraction systems, with different physical properties, were selected for the experiment: 4, 30, and 50 % (v/v) TBP/kerosene-Water. Within the range where the dispersed phase and continuous velocities vary from 1.47 × 10−3 m/s to 2.51 × 10−3 m/s, and the gas velocity ranges from 2.36 × 10−3 m/s to 1.18 × 10−3 m/s (note the order of these velocities should be clearly distinguished if they represent different phases). The droplet size (d32), dispersed-phase holdup (xd), and gas holdup (xg) were investigated in a disc-and-doughnut column (DDC) equipped with a gas-input unit. The aim of this investigation was to understand the influence of gas energy-input on hydrodynamic parameters. The results show that gas-input can expand flooding limitation, and it has the ability to break-up droplets, reducing droplets diameter from 3.6 mm to 1.2 mm approximately, while effectively preventing excessive fragmentation. The value of xd initially decreases and then increases with the increase in gas velocity. Within the operating gas velocity range, the value of xg increases from 9.7 % to 22.3 %, but without the effect of two-phase velocity. The modified correlations for droplet diameter, dispersed phase holdup, and gas holdup in the gas-agitated extraction column were proposed with deviations of 11.6 %, 15.9 %, and 4.3 %, respectively. These findings are useful to strengthen the low interfacial tension extraction processes in the future. A preliminary study was conducted to investigate the mass transfer enhancement in a gas-agitated column with a typical low interfacial tension extraction system (P204/kerosene-acidic solution of nickel cobalt complex hydroxide). Under similar conditions, extraction with P204/kerosene shows the improvement of metal extraction efficiency with an increase in gas velocity for agitation. The extraction efficiencies of Mg2+ and Mn2+ were significantly higher when gas-agitated was employed compared to pulsation. This finding indicates that gas-agitated column with moderate energy input is more suitable for low interfacial tension systems.
{"title":"Investigation of hydrodynamics behavior in a gas-agitated disc and doughnut column for solvent extraction with application to impurity removal from mixed nickel‑cobalt hydroxide precipitate","authors":"Chi Wang ,&nbsp;Dongbing Xu ,&nbsp;Boren Tan ,&nbsp;Chao Chang ,&nbsp;Chenye Wang ,&nbsp;Yong Wang ,&nbsp;Peng Xing ,&nbsp;Huiquan Li ,&nbsp;Xiahui Gui ,&nbsp;Jianguo Yang","doi":"10.1016/j.hydromet.2025.106438","DOIUrl":"10.1016/j.hydromet.2025.106438","url":null,"abstract":"<div><div>Controlling the dispersed phase droplet size within a reasonable range in the extraction column is crucial for enhancing mass transfer efficiency. Traditional high energy-inputs may result in excessive droplet fragmentation in low interfacial tension systems, posing significant challenges in intensifying the extraction process. This work proposes a novel gas-agitated technology to prevent excessive droplet fragmentation. Three extraction systems, with different physical properties, were selected for the experiment: 4, 30, and 50 % (<em>v</em>/v) TBP/kerosene-Water. Within the range where the dispersed phase and continuous velocities vary from 1.47 × 10<sup>−3</sup> m/s to 2.51 × 10<sup>−3</sup> m/s, and the gas velocity ranges from 2.36 × 10<sup>−3</sup> m/s to 1.18 × 10<sup>−3</sup> m/s (note the order of these velocities should be clearly distinguished if they represent different phases). The droplet size (<em>d</em><sub>32</sub>), dispersed-phase holdup (<em>x</em><sub>d</sub>), and gas holdup (<em>x</em><sub>g</sub>) were investigated in a disc-and-doughnut column (DDC) equipped with a gas-input unit. The aim of this investigation was to understand the influence of gas energy-input on hydrodynamic parameters. The results show that gas-input can expand flooding limitation, and it has the ability to break-up droplets, reducing droplets diameter from 3.6 mm to 1.2 mm approximately, while effectively preventing excessive fragmentation. The value of <em>x</em><sub>d</sub> initially decreases and then increases with the increase in gas velocity. Within the operating gas velocity range, the value of <em>x</em><sub>g</sub> increases from 9.7 % to 22.3 %, but without the effect of two-phase velocity. The modified correlations for droplet diameter, dispersed phase holdup, and gas holdup in the gas-agitated extraction column were proposed with deviations of 11.6 %, 15.9 %, and 4.3 %, respectively. These findings are useful to strengthen the low interfacial tension extraction processes in the future. A preliminary study was conducted to investigate the mass transfer enhancement in a gas-agitated column with a typical low interfacial tension extraction system (P204/kerosene-acidic solution of nickel cobalt complex hydroxide). Under similar conditions, extraction with P204/kerosene shows the improvement of metal extraction efficiency with an increase in gas velocity for agitation. The extraction efficiencies of Mg<sup>2+</sup> and Mn<sup>2+</sup> were significantly higher when gas-agitated was employed compared to pulsation. This finding indicates that gas-agitated column with moderate energy input is more suitable for low interfacial tension systems.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"233 ","pages":"Article 106438"},"PeriodicalIF":4.8,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143159455","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
The role of hydrogen peroxide in the acid dissolution of indium tin oxide (ITO) in the context of selective indium recovery from secondary sources
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2025-01-18 DOI: 10.1016/j.hydromet.2025.106437
Daísa C.A. Gonçalves , Daniel Majuste
This paper presents a thermodynamic, kinetic, and mechanistic examination of indium and tin extraction from indium tin oxide (ITO) in acidic sulfate solutions containing hydrogen peroxide (H2O2). The experimental approach included a comprehensive characterization of commercial ITO powder and leach residues by different techniques, as well as a systematic investigation of the effects of temperature, sulfuric acid (H2SO4) concentration, and hydrogen peroxide concentration on the leaching behavior (yield and rate) of indium and tin. The leaching tests showed that the presence of H2O2 in the H2SO4 solutions results in a significant increase in the leaching of indium, primarily at moderate temperatures. Furthermore, an increase in the H2O2 concentration in the solutions leads to a decrease in the concentration of tin in the leach liquor. The extraction of indium from ITO appears to occur in two steps. The first step involves the spontaneous hydration of In2O3 to form indium(III) hydroxide, In(OH)3, while the second step is the attack of this phase by protons (H+) to form soluble In3+ species, which is also a spontaneous reaction. The rate-determining step of indium extraction from fine ITO particles (mean particle size = 18 μm) is likely the diffusion of H+ through the pores of hydrated In2O3 particles and the grains of SnO2 surrounding these particles. With regard to the extraction of tin, the following sequence of steps was proposed: (i) the spontaneous reduction of the SnO2 phase in the acid solutions to Sn2+ by the active hydroperoxyl (HOO) radical, which is formed from the decomposition reaction of H2O2; (ii) the spontaneous oxidation of Sn2+ ions to Sn4+ by the oxygen molecules and the active hydroxyl (HO) radical, which are also formed from the decomposition reaction of H2O2; and (iii) the spontaneous precipitation of SnO2 from the unstable Sn4+ ions. A better understanding of the kinetics and mechanism of ITO dissolution in the H2SO4-H2O2 media may be helpful in the design and improvement of leaching processes targeting high indium recovery by selective leaching.
{"title":"The role of hydrogen peroxide in the acid dissolution of indium tin oxide (ITO) in the context of selective indium recovery from secondary sources","authors":"Daísa C.A. Gonçalves ,&nbsp;Daniel Majuste","doi":"10.1016/j.hydromet.2025.106437","DOIUrl":"10.1016/j.hydromet.2025.106437","url":null,"abstract":"<div><div>This paper presents a thermodynamic, kinetic, and mechanistic examination of indium and tin extraction from indium tin oxide (ITO) in acidic sulfate solutions containing hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>). The experimental approach included a comprehensive characterization of commercial ITO powder and leach residues by different techniques, as well as a systematic investigation of the effects of temperature, sulfuric acid (H<sub>2</sub>SO<sub>4</sub>) concentration, and hydrogen peroxide concentration on the leaching behavior (yield and rate) of indium and tin. The leaching tests showed that the presence of H<sub>2</sub>O<sub>2</sub> in the H<sub>2</sub>SO<sub>4</sub> solutions results in a significant increase in the leaching of indium, primarily at moderate temperatures. Furthermore, an increase in the H<sub>2</sub>O<sub>2</sub> concentration in the solutions leads to a decrease in the concentration of tin in the leach liquor. The extraction of indium from ITO appears to occur in two steps. The first step involves the spontaneous hydration of In<sub>2</sub>O<sub>3</sub> to form indium(III) hydroxide, In(OH)<sub>3</sub>, while the second step is the attack of this phase by protons (H<sup>+</sup>) to form soluble In<sup>3+</sup> species, which is also a spontaneous reaction. The rate-determining step of indium extraction from fine ITO particles (mean particle size = 18 μm) is likely the diffusion of H<sup>+</sup> through the pores of hydrated In<sub>2</sub>O<sub>3</sub> particles and the grains of SnO<sub>2</sub> surrounding these particles. With regard to the extraction of tin, the following sequence of steps was proposed: (i) the spontaneous reduction of the SnO<sub>2</sub> phase in the acid solutions to Sn<sup>2+</sup> by the active hydroperoxyl (HOO<sup>•</sup>) radical, which is formed from the decomposition reaction of H<sub>2</sub>O<sub>2</sub>; (ii) the spontaneous oxidation of Sn<sup>2+</sup> ions to Sn<sup>4+</sup> by the oxygen molecules and the active hydroxyl (HO<sup>•</sup>) radical, which are also formed from the decomposition reaction of H<sub>2</sub>O<sub>2</sub>; and (iii) the spontaneous precipitation of SnO<sub>2</sub> from the unstable Sn<sup>4+</sup> ions. A better understanding of the kinetics and mechanism of ITO dissolution in the H<sub>2</sub>SO<sub>4</sub>-H<sub>2</sub>O<sub>2</sub> media may be helpful in the design and improvement of leaching processes targeting high indium recovery by selective leaching.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"233 ","pages":"Article 106437"},"PeriodicalIF":4.8,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143159761","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
A novel method for leaching rare earth element from fluorescent lamp waste via acid fusion 通过酸融合从荧光灯废料中萃取稀土元素的新方法
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2024-11-14 DOI: 10.1016/j.hydromet.2024.106420
Guilherme Vieira Vaz , Fernanda Veronesi Marinho Pontes , Lucas André Bezerra Salgado , Manuel Castro Carneiro , Jéssica Frontino Paulino
Spent fluorescent lamps are alternatives to primary sources of rare earth elements. For recycling, the most common hydrometallurgical processes involve leaching with mineral acids, combined or not with alkaline fusion, which must be followed by another acidic leaching step for terbium, cerium, and lanthanum recovery. This study proposes a novel method employing acid fusion with potassium pyrosulfate (K2S2O7) and leaching with water at 25 °C. A full factorial design (23) was employed to study the following variables for the fusion process: temperature (450–550 °C), flux/sample mass ratio (2.2–3.0), and time (30–120 min). Under the optimal experimental conditions, the maximum recovery for La was 56.0 %. Recoveries were close to or greater than 70 % for Y, Ce, Eu, and Tb, at lower temperatures compared to those used in alkaline fusion, without the need for additional reagents and heating in the REE leaching step after fusion.
废荧光灯是稀土元素主要来源的替代品。在回收利用方面,最常见的湿法冶金工艺是用矿物酸浸出,无论是否结合碱熔,都必须再经过一个酸性浸出步骤才能回收铽、铈和镧。本研究提出了一种新方法,即使用焦硫酸钾(K2S2O7)进行酸熔,并在 25 °C 下用水浸出。采用全因子设计法(23)研究了熔融过程的以下变量:温度(450-550 ℃)、通量/样品质量比(2.2-3.0)和时间(30-120 分钟)。在最佳实验条件下,La 的最大回收率为 56.0%。与碱性熔融法相比,在较低的温度下,Y、Ce、Eu 和 Tb 的回收率接近或超过 70%,而无需在熔融后的 REE 沥滤步骤中使用额外的试剂和加热。
{"title":"A novel method for leaching rare earth element from fluorescent lamp waste via acid fusion","authors":"Guilherme Vieira Vaz ,&nbsp;Fernanda Veronesi Marinho Pontes ,&nbsp;Lucas André Bezerra Salgado ,&nbsp;Manuel Castro Carneiro ,&nbsp;Jéssica Frontino Paulino","doi":"10.1016/j.hydromet.2024.106420","DOIUrl":"10.1016/j.hydromet.2024.106420","url":null,"abstract":"<div><div>Spent fluorescent lamps are alternatives to primary sources of rare earth elements. For recycling, the most common hydrometallurgical processes involve leaching with mineral acids, combined or not with alkaline fusion, which must be followed by another acidic leaching step for terbium, cerium, and lanthanum recovery. This study proposes a novel method employing acid fusion with potassium pyrosulfate (K<sub>2</sub>S<sub>2</sub>O<sub>7</sub>) and leaching with water at 25 °C. A full factorial design (2<sup>3</sup>) was employed to study the following variables for the fusion process: temperature (450–550 °C), flux/sample mass ratio (2.2–3.0), and time (30–120 min). Under the optimal experimental conditions, the maximum recovery for La was 56.0 %. Recoveries were close to or greater than 70 % for Y, Ce, Eu, and Tb, at lower temperatures compared to those used in alkaline fusion, without the need for additional reagents and heating in the REE leaching step after fusion.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"232 ","pages":"Article 106420"},"PeriodicalIF":4.8,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142723435","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
Efficient separation and recovery of cobalt from grinding waste of cemented carbide using a sulfuric acid-sodium persulfate mixed solution 利用硫酸-过硫酸钠混合溶液从硬质合金研磨废料中高效分离和回收钴
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2024-11-06 DOI: 10.1016/j.hydromet.2024.106419
Shufen Liu, Shichang Song, Kai Tang, Longgang Ye
The mechanical processing of cemented carbide often generates a considerable amount of grinding waste from cemented carbide (GWCC), which serves as an important secondary resource for recovering Co and W. However, efficient separation of tungsten carbide (WC) and Co from GWCC remains challenging. This study tested an efficient process for separating Co from GWCC using a mixed solution of H2SO4-Na2S2O8. Under optimum conditions of 20 g/L H2SO4, 30 g/L Na2S2O8, 60 °C, and 1 h, the leaching efficiency of Co reached 97.0 %, compared to only 58.6 % when using H2SO4 alone. The kinetics of Co leaching in H2SO4 and H2SO4-Na2S2O8 solutions were determined to be a combination of chemical reaction control and diffusion control, suggesting that Co leaching rate in H2SO4 solution is significantly enhanced by introducing Na2S2O8. Finally, complete recovery of Co was achieved, and pure Co powder with a flower-cluster morphology was prepared from the leaching solution through oxalic acid precipitation followed by vacuum pyrolysis. The regenerative WC and Co powder can be recycled for cemented carbide production.
硬质合金的机械加工通常会产生大量的硬质合金研磨废料(GWCC),这些废料是回收钴和钨的重要二次资源。本研究测试了一种使用 H2SO4-Na2S2O8 混合溶液从 GWCC 中分离出 Co 的高效工艺。在 20 g/L H2SO4、30 g/L Na2S2O8、60 °C 和 1 小时的最佳条件下,钴的浸出效率达到 97.0%,而单独使用 H2SO4 时仅为 58.6%。H2SO4 和 H2SO4-Na2S2O8 溶液中的钴浸出动力学被确定为化学反应控制和扩散控制的结合,表明引入 Na2S2O8 后,H2SO4 溶液中的钴浸出率显著提高。最后,通过草酸沉淀和真空热解,实现了钴的完全回收,并从浸出液中制备出具有花簇形态的纯钴粉。再生 WC 和 Co 粉可循环用于硬质合金生产。
{"title":"Efficient separation and recovery of cobalt from grinding waste of cemented carbide using a sulfuric acid-sodium persulfate mixed solution","authors":"Shufen Liu,&nbsp;Shichang Song,&nbsp;Kai Tang,&nbsp;Longgang Ye","doi":"10.1016/j.hydromet.2024.106419","DOIUrl":"10.1016/j.hydromet.2024.106419","url":null,"abstract":"<div><div>The mechanical processing of cemented carbide often generates a considerable amount of grinding waste from cemented carbide (GWCC), which serves as an important secondary resource for recovering Co and W. However, efficient separation of tungsten carbide (WC) and Co from GWCC remains challenging. This study tested an efficient process for separating Co from GWCC using a mixed solution of H<sub>2</sub>SO<sub>4</sub>-Na<sub>2</sub>S<sub>2</sub>O<sub>8</sub>. Under optimum conditions of 20 g/L H<sub>2</sub>SO<sub>4</sub>, 30 g/L Na<sub>2</sub>S<sub>2</sub>O<sub>8</sub>, 60 °C, and 1 h, the leaching efficiency of Co reached 97.0 %, compared to only 58.6 % when using H<sub>2</sub>SO<sub>4</sub> alone. The kinetics of Co leaching in H<sub>2</sub>SO<sub>4</sub> and H<sub>2</sub>SO<sub>4</sub>-Na<sub>2</sub>S<sub>2</sub>O<sub>8</sub> solutions were determined to be a combination of chemical reaction control and diffusion control, suggesting that Co leaching rate in H<sub>2</sub>SO<sub>4</sub> solution is significantly enhanced by introducing Na<sub>2</sub>S<sub>2</sub>O<sub>8</sub>. Finally, complete recovery of Co was achieved, and pure Co powder with a flower-cluster morphology was prepared from the leaching solution through oxalic acid precipitation followed by vacuum pyrolysis. The regenerative WC and Co powder can be recycled for cemented carbide production.</div></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":"231 ","pages":"Article 106419"},"PeriodicalIF":4.8,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142658786","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
Preparation of high-purity iron oxide from end-of-life NdFeB magnet waste 利用报废钕铁硼磁铁废料制备高纯度氧化铁
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2024-11-06 DOI: 10.1016/j.hydromet.2024.106418
Zhouyi Chai , Minglu Rao , Bin Wen , Li Huang , Haopeng Zhang , Yanfei Xiao
The acid-soluble residue from end-of-life NdFeB magnet waste is often introduced into the ferrous metallurgical process to recover iron oxide as a value added product, but this approach has a low economic value. In this work, a ferrous chloride solution from NdFeB magnet waste containing rare earth elements, which was obtained after the leaching and impurity removal process from the acid-soluble residue, was used as the raw material. The crystallization mechanism and reaction kinetics in the oxidation precipitation process were studied to prepare high-purity iron oxide. The results showed that the growth of γ-FeOOH flakes with smooth surfaces and uniform morphologies could be explained by Ostwald's ripening theory. The apparent activation energy of the oxidative precipitation reaction of ferrous iron was 56.8 kJ/mol, indicating a chemically controlled reactions. Under the optimal oxidative precipitation conditions, the precipitation efficiency of ferrous ions and rare earth elements was 98.8 % and < 1 %, respectively. The precipitated product was well-crystallized γ-FeOOH with an aggregated flake morphology. It was roasted at 700 °C for 2 h to obtain an iron oxide product with a purity of 99.6 %. This study could provide technical support for the valuable utilization of acid-soluble residues from NdFeB magnet waste and to propose new methods for the utilization of other iron wastes and residues.
报废钕铁硼磁铁废料中的酸溶性残渣通常会被引入黑色冶金工艺,以回收氧化铁作为增值产品,但这种方法的经济价值较低。本研究以钕铁硼磁体废料中含有稀土元素的氯化亚铁溶液为原料,该溶液是从酸溶性残渣中经过浸出和除杂工艺得到的。研究了氧化沉淀过程中的结晶机理和反应动力学,以制备高纯度氧化铁。结果表明,奥斯特瓦尔德熟化理论可以解释表面光滑、形态均匀的γ-FeOOH薄片的生长。亚铁氧化沉淀反应的表观活化能为 56.8 kJ/mol,表明这是一种化学控制反应。在最佳氧化沉淀条件下,亚铁离子和稀土元素的沉淀效率分别为 98.8 % 和 < 1 %。沉淀产物是结晶良好的γ-FeOOH,具有聚集片状形态。在 700 °C 下焙烧 2 小时后,得到纯度为 99.6 % 的氧化铁产品。这项研究可为有价值地利用钕铁硼磁铁废料中的酸溶性残留物提供技术支持,并为利用其他铁废料和残留物提出新方法。
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引用次数: 0
Separation of cerium from solution by oxidative precipitation with hydrogen peroxide: The reaction mechanism 用过氧化氢氧化沉淀法从溶液中分离铈:反应机理
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2024-11-03 DOI: 10.1016/j.hydromet.2024.106417
Georgiana Moldoveanu, Vladimiros Papangelakis
Cerium removal from solution via oxidative precipitation with hydrogen peroxide was investigated in a batch reactor to identify optimum conditions for maximum Ce removal. Tests were performed under ambient temperature at pH 2, 3, 4 and 5, using the exact stoichiometric requirement and 30 % and 50 % excess, respectively. It was found that, unlike the usual direct Ce(OH)4 formation presented in the literature for most oxidants, the reaction with hydrogen peroxide proceeded via a metastable ceric hydroxide, with conversion rates increased by increasing temperature. Standard free energies of reaction were calculated for both routes. To better understand the process, the oxidation of Ce(III) to Ce(IV) and the precipitation of Ce(OH)4 were studied separately via a decoupled approach at low pH and reaction mechanisms for each process were proposed. The Ce(III) oxidation reaction was identified as the rate-limiting step, whereas Ce(IV) precipitation was fast and quantitative. In the pH range of 3–5, Ce removal extents varied between 80 and 95 %, depending on the hydrogen peroxide excess. Following the Ce removal step via oxidative precipitation, it was found that a 2 h ageing stage at 80 °C and pH 2.5 was required to complete the transition of cerium hydroxy-peroxide to the more stable ceric hydroxide and decompose any residual H2O2.
研究人员在间歇式反应器中研究了通过过氧化氢氧化沉淀从溶液中去除铈的方法,以确定最大程度去除铈的最佳条件。试验是在 pH 值为 2、3、4 和 5 的环境温度下进行的,分别采用了精确的化学计量要求以及 30% 和 50% 的过量。结果发现,与文献中大多数氧化剂通常直接形成 Ce(OH)4 的情况不同,与过氧化氢的反应是通过一种可转移的氢氧化铈进行的,温度升高,转化率增加。对两种途径的标准反应自由能进行了计算。为了更好地理解这一过程,在低 pH 值条件下,通过解耦方法分别研究了 Ce(III) 氧化成 Ce(IV) 和 Ce(OH)4 沉淀的过程,并提出了每个过程的反应机制。研究发现,Ce(III) 氧化反应是限速步骤,而 Ce(IV) 沉淀则是快速定量反应。在 pH 值为 3-5 的范围内,Ce 的去除率在 80% 到 95% 之间,具体取决于过氧化氢的过量。在通过氧化沉淀进行除铈步骤后,发现需要在 80 °C 和 pH 值为 2.5 的条件下进行 2 小时的老化阶段,以完成过氧化氢铈向更稳定的氢氧化铈的转变,并分解任何残留的 H2O2。
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引用次数: 0
Phase evolution and elemental distribution of zinc and germanium during the sulfide roasting, zinc fuming and leaching processes: Benefit of pretreating zinc oxide dust 硫化物焙烧、锌发烟和浸出过程中锌和锗的相变和元素分布:氧化锌粉尘预处理的益处
IF 4.8 2区 材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2024-10-29 DOI: 10.1016/j.hydromet.2024.106416
Yundong Zhu , Xilin Geng , Jiankang Wen , Wei Qu , Liangshi Wang
Germanium plays an essential role in many high-tech fields because of its excellent electrical and optical properties. As a zinc refining by-product, zinc oxide dust (ZOD) is one of the most important sources of germanium recovery. However, the low leaching efficiency of germanium seriously hinders germanium recovery. This study focuses on the phase evolution and elemental distribution of zinc and germanium during the zinc refining process by analyzing the occurrence state of zinc and germanium in products and the key factors and chemical reactions causing the loss of zinc and germanium during the process. In the sulfuric-acid leaching process without an oxidant, the sulfides encapsulating germanium cannot be leached, which resulted in a loss of germanium. In addition, the formation of an insoluble PbSO4 coating layer and silica compounds during the sulfuric-acid leaching impeded the leaching reactions. Accordingly, pre-treatment by oxidative leaching with Fe3+ and the role of NaAc in dissolving PbSO4 were tested. The efficiency of Ge recovery is approximately 30 % higher than that of the conventional leaching process.
锗因其优异的电气和光学特性,在许多高科技领域发挥着重要作用。作为锌精炼的副产品,氧化锌粉尘(ZOD)是锗回收的重要来源之一。然而,锗的低浸出效率严重阻碍了锗的回收。本研究通过分析锌和锗在产品中的出现状态,以及在锌精炼过程中造成锌和锗损失的关键因素和化学反应,重点研究了锌精炼过程中锌和锗的相演变和元素分布。在没有氧化剂的硫酸浸出过程中,包裹锗的硫化物无法被浸出,从而导致锗的损失。此外,硫酸浸出过程中形成的不溶性 PbSO4 涂层和二氧化硅化合物也阻碍了浸出反应。因此,测试了用 Fe3+ 进行氧化浸出的预处理以及 NaAc 在溶解 PbSO4 中的作用。Ge 的回收效率比传统浸出工艺高出约 30%。
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引用次数: 0
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Hydrometallurgy
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