Recycling of nickel–metal hydride batteries. II: Electrochemical deposition of cobalt and nickel

A combination of hydrometallurgical and electrochemical processes has been developed for the separation and recovery of nickel and cobalt from cylindrical nickel–metal hydride rechargeable batteries. Leaching tests revealed that a 4 mol dm^?3 hydrochloric acid solution at 95 °C was suitable to dissolve all metals from the battery after 3 h dissolution. The rare earths were separated from the leaching solution by solvent extraction with 25% bis(2‐ethylhexyl)phosphoric acid (D2EHPA) in kerosene. The nickel and cobalt present in the aqueous phase were subjected to electrowinning. Galvanostatic tests on simulated aqueous solutions investigated the effect of current density, pH, and temperature with regard to current efficiency and deposit composition and morphology. The results indicated that achieving an Ni? Co composition with desirable properties was possible by varying the applied current density. Preferential cobalt deposition was observed at low current densities. Galvanostatic tests using solutions obtained from treatment of batteries revealed that the aqueous chloride phase, obtained from the extraction, was suitable for recovery of nickel and cobalt through simultaneous electrodeposition. Scanning electron micrography and X‐ray diffraction analysis gave detailed information of the morphology and the crystallographic orientation of the obtained deposits. Copyright © 2004 Society of Chemical Industry     

Recycling rare-earth-metal waste using hydrometallurgical methods

The present review describes the state of the problem of extracting rare earth metals from secondary raw materials, such as high-coercivity magnets, nickel–metal hydride batteries (NiMH), and phosphors of coatings of fluorescent lamps. Methods for waste processing with mineral acids and other solvents, the removal of associated impurities from rare-earth components, separation, and deep purification (mainly by solvent extraction) have been considered. Data on the industrial applications of hydrometallurgical processes for rare earth metals recycling have been presented.     

Selective recovery of cobalt from the cathode materials of NMC type Li-ion battery by ultrasound-assisted acid leaching and microemulsion extraction

ABSTRACT

A selective recovery process for cobalt from the cathode materials of Li-ion batteries is demonstrated in this report. First, acid leaching was applied to dissolve the metals from the lithium-metal oxides. It was found out that with the assistance of probe type ultrasonication, manganese could be simultaneously separated by precipitation. This phenomenon would reduce the difficulty for later separation. Next, water-in-oil microemulsion extraction was applied for direct extraction of cobalt from the other metals. The cobalt extraction yield was 98% and purity was 96%. Moreover, the microemulsion system could be reused for 100 times without losing its extraction ability.     

The separation and recovery of copper(Ⅱ), nickel(Ⅱ), cobalt(Ⅱ), zinc(Ⅱ),and cadmium(Ⅱ) in a sulfate-based solution using a mixture of Versatic 10 acid and Mextral 984H

We studied the separation and recovery of copper(Ⅱ), nickel(Ⅱ), cobalt(Ⅱ), zinc(Ⅱ), and cadmium(Ⅱ) from magnesium and calcium, using synergistic solvent extraction(SSX) in a typical hydrometallurgical waste solution. A mixture of Versatic 10 acid and Mextral 984 H, diluted with Mextral DT100, was used to obtain fundamental data on p H and distribution isotherms, as well as the kinetics of extraction and stripping. We also investigated the main effects and interactions of common solvent extraction factors: the extraction p H at equilibrium, the temperature, and the extractant concentration. The synergistic effect for extracting metals was confirmed. The results showed that the addition of Mextral 984 H enhanced the separation factors of copper, nickel, cobalt,zinc, and cadmium over magnesium and calcium. Compared with Versatic 10 acid alone, for a mixture of0.5 mol·L~(-1) Versatic 10 acid/0.5 mol·L~(-1)Mextral 984 H, Δp H50 values of copper, nickel, cobalt, zinc, and cadmium were found to be N 2.0, 3.30, 2.85, 0.95, and 1.32 p H units, respectively. The Δp H_(50)(Zn–Mg)and Δp H_(50)(Zn–Ca)values were 3.27 and 2.25, respectively, indicating easy separation and recovery of copper, nickel, zinc, cobalt,and cadmium. The extraction and stripping of copper, cobalt, zinc, and cadmium were fast, with 90% of the metal transferred in 2 min. We next studied whether the metals could be stripped from the extracted liquid selectively in sequence, by using sulfuric acid at different concentrations. The influence of the molecular structure of the oxime and carboxylic acid components upon the synergistic effects was identified by numerical analysis.Excellent separation of copper, nickel, cobalt, and zinc over magnesium and calcium was achieved with this synergistic solvent extraction system.     

Recovery of nickel from spent catalysts using ultrasonication‐assisted leaching

BACKGROUND: Solid catalysts containing metals or metal oxides play a key role in the chemical process industries to produce valuable products and fuels and consequently are left as solid wastes after a certain period of use. Disposal of these spent catalysts requires compliance with stringent environmental regulations because of their hazardous nature and content of toxic chemicals. Therefore recovery of the metals by various methods has been explored. In the present study recovery of nickel from spent nickel catalysts using ultrasonication‐assisted leaching has been investigated. RESULT: The effect on nickel recovery of acid concentration, temperature, solid to liquid (S:L) ratio, and time of digestion were studied in detail and optimized for the ultrasonication route. The results obtained are compared with the chelation route and conventional acid leaching technique. Using ultrasonication‐assisted leaching 95% extraction of nickel was achieved at 90 °C, 40% nitric acid concentration and S:L ratio 1:10 (g:mL) in 50 min from the spent nickel–alumina catalysts. CONCLUSION: Using an ultrasonication technique 95% recovery of nickel was significantly faster (50 min) than the chelation route (7 h), while with conventional acid leaching a maximum of 93% nickel recovery was obtained in 9 h. Compared with conventional acid leaching the purity of leached nickel salts was good and they could be recycled for the preparation of fresh catalysts after removing Al impurities. Copyright © 2011 Society of Chemical Industry     

低共熔溶剂在废旧锂离子电池正极材料回收中的研究进展

大规模储能与电动汽车市场的发展壮大对锂离子电池的需求水涨船高,由此产生的废旧锂离子电池数量也即将迎来爆发式增长。废旧锂离子电池正极材料蕴含丰富的锂、钴、镍、锰等有价金属元素,回收经济价值高,环境效益显著。低共熔溶剂（DESs）作为一种绿色溶剂,在废旧锂离子电池有价金属元素回收方面显示出巨大的潜力。本文在简要介绍DESs性质及应用的基础上,系统综述了DESs在废旧锂离子电池正极材料回收链中的研究现状,主要包括正极材料的分离、活性物质的浸出以及有价金属的提取,着重介绍了现阶段回收的方法及工艺流程,比较了不同DESs浸出正极活性物质的优缺点,探讨了当前DESs在废旧锂离子电池回收中的共性问题,并展望了未来DESs回收锂离子电池的发展方向。     

镍基含铼废合金氧化酸浸工艺

在硫酸体系中,采用熔融雾化制粉、硫酸体系双氧水氧化酸浸工艺浸出铼,钨钽等稀有金属富集在渣中,研究了酸度、双氧水用量、温度、粒度、液固体积/质量比、时间对浸出的影响. 结果表明,最佳浸出条件为：在硫酸体系中,废合金雾化粉20 g,粉末粒度71~100 mm,温度75℃,液固比8 mL/g,硫酸浓度3.5 mol/L,滴加30%双氧水65 mL,反应6 h. 该条件下铼、镍和钴的浸出率均超过99%,钨钽浸出率均低于1%,钼浸出率为28%,实现了铼浸出与稀有金属在渣中富集.     

从钴镍切削废料中回收有价金属的方法

研究了以钴、镍合金切削废料为原料，通过酸溶、除铁、除铬、钴镍分离等过程，回收有价金属氧化钴、氢氧化镍的工艺条件，通过生产实践，确定了最佳工艺条件及生产工艺，得到的产品质量分别达到国家标准和企业标准。     

Recovery of nickel from spent catalyst from palm oil hydrogenation process using acidic solutions

In this study, recovery of nickel from spent catalyst from palm oil hydrogenation process is carried out via extractive leaching process using sulfuric and hydrochloric acids. The effects of acid concentration, solid-liquid ratio, temperature and digestion time on the recovery (acid dissolution) process are investigated. It is found that sulfuric acid is the better leaching solution as compared to hydrochloric acid for recovery (dissolution) of nickel from the spent catalyst. Results from speciation modelling using VMINTEQ further imply that nickel can form sulfate complexes which are more stable than chloride complexes at concentrations higher than 1 M. The optimum conditions for maximum recovery at 85% are achieved at 67% sulfuric acid concentration, digestion time of 140 min, solid-to-liquid ratio of 1:14 and reaction temperature of 80 °C. At solution temperatures higher than 80 °C, the percentage nickel extraction is reduced. The optimization study presented here is useful for spent catalyst generators in the palm oil industry intending to recover valuable metals which may assist in reducing palm oil processing costs.     

包钢选矿厂尾矿中稀土与铁共提取

研究了包钢选矿厂尾矿经稀硫酸-稀盐酸溶解、溶解液在乙醇作用下结晶共提取稀土与铁的新工艺. 实验考察了稀硫酸溶解稀土尾矿时,溶解温度、硫酸浓度等对稀土和铁溶解率的影响. 最佳条件下稀硫酸溶解液中稀土溶解率低于8%,铁的溶解率大于94%. Fe3+经工业铁屑还原为Fe2+,在室温下用乙醇提取FeSO4,FeSO4纯度为98.21%,尾矿中铁回收率达89.51%. 稀盐酸不溶物中稀土氧化物(REO)品位为43.60%,稀土回收率达78.82%,新工艺实现了稀土和铁资源的提取分离.     

Separation and Recovery of Valuable Metals from Nickel Slags Disposed in Landfills

With the increased requests for more sustainable extraction processes feedstocks with low metal content are becoming more attractive. In this research, an additional refining step is investigated in order to recover valuable metals from slag generated during nickel extraction process, particularly copper, nickel, and cobalt. Slag was settled at the different temperatures for various times in conditions that simulated the industrial environment. The chemical composition and morphology of newly formed matte and slag were determined. Kinetic parameters of matte formation, valuable metal recovery rates and partition coefficients were deduced. Metals separation and settling rate was found to be strongly dependent on temperature. The highest recovery rates were found to occur at 1598 K (1325°C) for two hour settling while the most economical combination of parameters was found when settling at 1573 K (1300°C) for one hour. Silica additions generated higher partition coefficients for copper and nickel than the addition of lime. It is concluded that an additional refining step involving SiO₂ and CaO fluxes is an economical way to recover more than 60% of valuable metals from slag that is disposed in landfills.     

湿法回收退役三元锂离子电池有价金属的研究进展

近年来，随着三元体系锂离子电池市场份额的快速增加，退役三元锂离子电池将在未来出现爆发式增长，因此，回收三元锂离子电池电极材料中高价值的钴、镍、锂等有价金属成为电池行业的又一研究热点。本文详述了湿法回收三元电池电极材料有价金属的工艺流程和主要方法，重点介绍了有价金属的浸取方法、金属的分离提取、再合成利用和浸取动力学机理的研究进展，比较了工艺流程中不同处理方法的优缺点。并对回收退役三元电池材料的有价金属作了经济性分析，结果表明，三元电池材料有价金属回收具有可观的经济效益。最后对湿法回收三元电池材料中的有价金属方法进行总结，并简述了未来湿法回收处理方法的重要技术，包括化学纯化、自动化拆解以及完善的分类回收技术等，为未来三元电池材料回收技术发展提供参考。     

Simultaneous Recovery of Nickel and Cobalt from Aqueous Solutions using Complexation-Ultrafiltration Process

Simultaneous recovery of nickel and cobalt from aqueous solutions by complexation-ultrafiltration process with polyethylenimine (PEI) was studied. Experiments were performed as a function of polymer/metal ratio (P/M), solution pH, and ionic strength. Effects of concentration time on metal rejection and membrane flux were also studied. At optimum experimental conditions of pH 6.0 and P/M 5.0, the nickel removal efficiency reaches at 99.9% and cobalt removal efficiency goes to 96.4%. Both nickel and cobalt removal efficiencies decreased as the adding salt concentration increases. During 12 h of the ultrafiltration process, the decline of membrane flux was less than 16% and the removal efficiencies for both nickel and cobalt were kept almost constant. Diafiltration was further performed to regenerate PEI. The removal efficiencies for both metals using recycled PEI were found to be close to those with the original PEI. Results from the two-step process of complexation-UF and decomplexation-UF separation showed that it could be a promising method for simultaneous recovery of nickel and cobalt from aqueous solutions.     

Simultaneous recovery of valuable metals from spent mobile phone battery by an acid leaching process

This research was carried out to recover some valuable metals from the electrodes of spent mobile phone batteries by leaching process in laboratory scale. Two types of spent mobile phone batteries were employed in this study: nickel-metal hydride (Ni-MH) and lithium-ion (Li-ion) batteries. Effects of parameters including types of acid (H₂SO₄, HNO₃ and HCl), acid concentration (1-6 M), solid-liquid ratio (10-40 g/l), leaching time (5-120 min) and leaching temperature (303-363 K) on the leaching percentages of Co and Ni were investigated. The preliminary results indicated that HCl provided higher leaching percentages than that of H₂SO₄ and HNO₃ for both metals at all leaching conditions. At optimum conditions, greater than 92% and 84% of Ni and Co were leached, respectively. Further investigation indicated that the leaching process of both metals was endothermic with the rate law of a second-order reaction and its kinetics was principally controlled by the physical process.     

低冰镍转炉渣中钴的氧压酸浸行为及其动力学

研究了转炉渣中钴氧压硫酸体系选择性浸出过程的行为及其动力学。通过改变搅拌速度、反应温度、硫酸浓度、氧分压、物料粒度以及反应时间等浸出条件,考察钴浸出率的变化及影响,获得转炉渣中钴的浸出动力学规律。结果表明,钴的浸出率随着温度、酸度、氧分压的增加而增加;硫酸质量浓度大于0.4 mol·L^-1会导致铁大量溶出;浸出过程符合未反应芯收缩核模型,前期受化学反应控制,然后转变为混合控制,后期受固体产物层扩散控制。化学反应控制和固体产物层扩散控制过程的活化能分别为43.19 kJ·mol^-1 和10.49 kJ·mol^-1。化学反应控制过程对硫酸浓度、氧分压及粒度的反应级数分别为0.79、0.85和 -0.95。     

Reagent Degradation in the Synergistic Solvent Extraction System LIX®63/Versatic™10/Nonyl-4PC

Direct solvent extraction of nickel and cobalt from nitrate-based leach liquors has become of interest due to the successful piloting of nitric acid processes for treating nickel laterite ores. The current study investigated the stability of both hydroxyoxime and nonyl-4PC (nonyl-4-pyridine carboxylate) in LIX 63/Versatic 10/nonyl-4PC under conditions relevant to the recovery of nickel and cobalt from a nitrate-based leach liquor with stripping into sulfuric acid. Nonyl-4PC increased both the rate of hydroxyoxime degradation under the pH 1.5 extract conditions required for a potential nickel–cobalt separation process and the rate of cobalt poisoning of LIX 63. Under strip conditions and the pH 4 extract conditions required for co-extraction of nickel and cobalt, nonyl-4PC did not otherwise affect the rate of hydroxyoxime loss. Additionally, the presence of nitrate anions did not increase the loss of either hydroxyoxime or nonyl-4PC. The combination LIX 63/Versatic 10/nonyl-4PC therefore appears prospective for the co-extraction of nickel and cobalt at pH 4 from nitrate-based leach liquors.     

金属氢化物-镍电池的回收与循环再利用

介绍了国内外废旧电池的回收概况以及火法和湿法回收金属氢化物 -镍电池的工艺流程。指出传统的火法或湿法回收工艺复杂 ,成本高 ,有价金属回收率低 ,且使用各种化学试剂又会对环境造成二次污染。提出在系统分析金属氢化物 -镍电池失效原因的基础上 ,探寻简单可行的非破坏性电池再生技术新途径     

Separation of Cobalt and Nickel with Phenylphosphonic Acid Mono-4-tert-octylphenyl Ester by Liquid Surfactant Membranes

Abstract

The separation of cobalt and nickel with liquid surfactant membranes (LSMs) was carried out in a stirred cell using a newly synthesized extractant. The effect of a surfactant on the kinetics of cobalt and nickel extraction was investigated to elucidate the role of a surfactant used in LSMs. The extraction equilibrium of these metals was also examined. Further, the interfacial tension between the organic and aqueous phases was measured to elucidate the adsorption equilibrium of a surfactant. It was found that the interfacial activity of the extractant is as high as that of a surfactant. In the extraction equilibrium study of these metals, extraction equilibrium constants were obtained for cobalt and nickel for the following equations:

Co²⁺ + 2(HR)₂=CoR₂(HR)₂ + 2H⁺ Ni²⁺ + 3(HR)₂=NiR₂2(HR)₂ + 2H⁺ The effects of the extractant and surfactant on the extraction rate of cobalt and nickel in LSMs were studied. The results were analyzed by a proposed model with an interfacial reaction, and rate constants were obtained for each metal. It was found that the new extractant has a very strong extractability for each metal compared with a conventional commercial extractant such as 2-ethylhexylphosphonic acid mono-2-elhylhexylester (commercial name, PC-88A) or di(2-ethylhexyl)phosphoric acid (D2EHPA). Further, a surfactant strongly affected the extraction rate and the separation of these metals, and a cationic surfactant was selected.     

Production of high purity rare earth mixture from iron-rich spent fluid catalytic cracking (FCC) catalyst using acid leaching and two-step solvent extraction process

Acid leaching and a two-step solvent extraction procedure were developed to produce high purity mixture of La and Ce from iron-rich spent FCC catalyst discharged from Dzung Quat refinery (Vietnam). Acid leaching of the spent catalyst with 2M HNO₃ and a solid-to-liquid ratio of 1/3 at 80 °C in 1 h dissolved almost 90% of La while 12% of Al and 25% of Fe were transferred to the leachate. The extraction of RE metals and main impurities such as Al and Fe by a mixture of di-2-ethylhexyl phosphoric acid (D2EHPA) and tributyl phosphate (TBP) was investigated. Experiments showed that it was necessary to remove Fe before extracting RE and the optimum extraction conditions for a high recovery of RE while 0% of Al extraction were pH-1, contact time=10min, and D2EHPA/TBP volume ratio= 4: 1. At these conditions, the extraction yields of La(III) and Ce(III) were 72% and 89%, respectively. A two-step solvent extraction was developed to achieve a high purity of RE mixture, which included (1) the removal of impurity Fe by 25% (v/v) diisooctyl phosphinic acid (DiOPA) in n-octane for 140 min, (2) the extraction of rare earths by a mixture of di-2-ethylhexyl phosphoric acid (D2EHPA) and tributyl phosphate (TBP) in n-octane for 10 min without the need for adjusting the pH of the leaching solution.     

镍火法冶炼废渣中钴、镍回收的研究进展

综述了镍火法冶炼废渣中钴、镍等有价金属资源综合回收技术.通过回顾镍火法冶炼过程中产生的典型废渣的物相研究以及渣中钴、镍等有价金属回收的研究现状,分析和讨论了主要处理镍冶炼废渣工艺的优势及存在的缺陷,展望了研究方向和趋势.指出选矿法尽管能够经济地实现钴、镍富集的目的,但存在原料适用范围狭窄的局限性;火法处理工艺存在能耗高,会产生气态污染物的缺陷;微生物浸出工艺存在反应速率低的问题,但具有工艺简单、投资少等优点,是极具发展前景的研究方向.氧压酸浸能够高选择性浸出钴、镍,钴、镍的回收率高,过程无有害废弃物产生,环境友好,是今后提取废渣中钴、镍的可取方法.炉渣缓冷、焙烧或还原预处理后再进行氧压酸浸,浸出过程中加入含镍的磁黄铁矿等尾矿替代硫酸作为浸出剂,是氧压浸出工艺的发展趋势.