共沉淀法制备镍、钴、锰复合碳酸盐的热力学分析

由共沉淀法合成了用于制备锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2的均匀的前驱体.通过对M2 (Ni2 ,Co2 ,Mn2 )-NH3-CO32--H2O体系的热力学分析,拟出了M2 -NH3-CO32--H2O体系中的lg[M2 ]-pH关系图(其中M为过渡金属元素).以NH4Cl为络合剂,以Na2CO3为沉淀剂,采用共沉淀法制备锂离子电池正极材料用镍、钴、锰复合碳酸盐,最佳共沉淀的pH值为8.0左右.在此pH值条件下由共沉淀法制备的镍、钴、锰复合碳酸盐前驱体类球形粉料的组分恒定,粒度分布均匀,中位粒径D50为11.78μm.     

氨-碳酸盐法分离PTA废渣中的钴和锰

精对苯二甲酸（PTA）生产中的废钴锰催化剂中钴低锰高,常用的钴锰分离方法一般不适用,分离钴锰时非常容易互相夹带,导致分离不完全。本文采用氨-碳酸盐法分离PTA废渣浸出液中的钴和锰。在正交试验的基础上,以钴剩余率和锰沉淀率作为考核指标,考察了碳酸盐的种类、反应时间、反应温度、搅拌速度、氨的用量和碳酸盐的用量等因素对钴、锰分离效果的影响。实验结果表明,在氨-碳酸钠、氨-碳酸铵、氨-碳酸氢铵3种溶液中,最佳搅拌速度、反应时间、反应温度分别为200r/min、8h和20℃,氨的最佳用量分别为理论化学反应计量的1.9倍、1.4倍和1.7倍,碳酸盐的用量分别为理论化学反应计量的1.0倍、1.3倍和1.3倍。在最佳反应条件下,氨-碳酸钠、氨-碳酸铵、氨-碳酸氢铵3种溶液中,钴的最大剩余率分别可达到96.0%、99.8%和99.5%,锰沉淀率均可达到100%。     

镍钴锰三元电池废料浸出液除铜铁净化

对镍钴锰三元废电池材料盐酸浸出液分离去除铜和铁杂质进行了研究. 采用铁粉置换法除铜,考察了铁粉用量、反应温度和反应时间等因素对铜脱除率及镍钴锰损失率的影响;除铜后浸出液采用针铁矿法除铁,考察了反应时间、反应温度及终点pH值对铁去除率和镍钴锰损失率的影响. 结果表明,铜和铁的去除率均在99%以上,镍、钴、锰的总损失率分别为2%, 3%, 2%. 净化后溶液满足制备合格镍钴锰三元系前驱体的要求.     

锂离子电池高钴正极片中镍的测定

研究了锂离子电池高钴正极片中常量镍的测定。以酒石酸掩蔽铁、钙、镁等杂质,在pH=5.5~6.0时以丁二酮肟沉淀分离镍,用盐酸溶解沉淀,所得溶液蒸发至近干以破坏丁二酮肟;在pH=10的氨-氯化铵缓冲溶液中以过氧化氢氧化返溶得到的镍液中残留的钴,用EDTA滴定镍。方法的回收率为97.56%~101.92%,RSD为0.56%。     

丁二酮肟重量法对泵轴中镍含量的测定

泵轴中镍的测定采用在乙酸铵缓冲溶液中,用酒石酸钾钠作络合剂,以硫代硫酸钠掩蔽铜,在pH值为6.0~6.4时,镍与丁二酮肟生成丁二酮肟镍沉淀,与铁、钴、铜、锰、铬、钼、钨、钒等元素分离,丁二酮肟镍沉淀经140±5℃烘干并称至恒重。     

含氮杂环化合物与有机酸协同体系在镍、钴萃取分离中的应用

近年来开发了多种含氮杂环化合物与有机酸类萃取剂的协同体系,明显提高了镍、钴的萃取性能,同时增强了对杂质元素的分离效果,具有较大的实际应用价值。本工作综述了一些具有代表性的含氮杂环化合物与有机酸类萃取剂组成的协同萃取体系,探讨了萃取体系对镍、钴的协同萃取效果及与常见杂质元素的分离,并讨论了协同萃取体系潜在的工业应用。协同体系对镍、钴的萃取及对杂质元素的分离主要是由酸性萃取剂本身性质和含氮杂环协萃剂的影响共同决定,有机磺酸、羧酸、膦酸等萃取剂与含氮杂环化合物组成的协同萃取体系在萃取镍、钴的过程中对金属杂质元素分离的选择性不同,在镍、钴的提取及生产过程中也展现出不同的应用价值。     

定性分析中铝镍组游子几种化学性状之图线表示法

在普通元素定性分析程序中,于银组及铜锡组分离后,用氢氧化铵及硫化铵沉淀之元素,以往称铁铝组,后改称铁锌组,最近之Noyes-Swift 氏定性分析又改称铝镍组,内包括铝,铬,锌,镍,钴铁及锰共七个元素。铝镍两组之分离,铝组及镍组中各元素之相互分离,常根据各个游子化学性状之差别以定分离之步骤。分离之步骤在合理的情形下可以随时更改,是以小组之名称亦可依之而变更。与该组中元素有关之化学性状,一为氢氧化物之溶度。其溶度积常数Ksp 愈小,则其沉淀易     

不锈钢老化着色液预还原草酸沉淀除杂过程研究

为实现不锈钢老化着色液杂质离子的分离与回收,采用预还原-草酸沉淀法对老化液中铁、镍、锰沉淀除杂过程进行研究。通过溶液化学计算及条件优化实验,考察铁、镍、锰离子沉淀效率,并使用X射线衍射仪、扫描电子显微镜、X射线光电子能谱仪对草酸沉淀物进行物相及形貌结构的表征。结果表明,通过控制溶液pH及草酸用量可有效实现溶液中铁离子、锰离子、镍离子与草酸根络合,形成草酸盐沉淀,实现杂质离子与溶液铬离子分离,杂质离子沉淀顺序依次为锰离子、镍离子、铁离子。老化液预还原后,在草酸过量系数为1.2、溶液pH为2、反应温度为25℃的条件下沉淀反应2 h,铁、锰、镍离子沉淀率分别可达98.12%、99.35%、87.26%,沉淀物主要为二水草酸亚铁及少量草酸镍、草酸锰。     

红土镍矿硝酸加压浸出工艺

采用硝酸介质加压浸出处理红土镍矿,考察了初始硝酸浓度、浸出温度、保温时间和液固比对有价组分浸出率的影响,确定了该工艺的可行性。得到优化工艺条件为初始硝酸浓度330 kg/t,浸出温度190℃,保温时间60 min,液固比1.5:1~1.7:1 mL/g。最优工艺条件下,镍、钴的浸出率均大于85%,镁浸出率为80%,铝的浸出率大于60%,铁的浸出率低于1%,产出了含铁55%的富铁渣。对浸出液采用氧化镁梯级沉淀的方法,控制温度85℃、pH?3.0,可除掉95%的铁;控制pH=4.0~4.3,可除掉99%以上的铝,原矿中约90%以上的钪随铝进入渣相,得到含钪近1000 g/t的铝钪富集物;调节pH=7.5~8.0,溶液中的镍钴沉淀完全,得到含镍24.8%和含钴2.3%的氢氧化镍钴渣,实现了镍、钴与铁、铝高效分离和富集。梯级沉淀后的硝酸镁溶液蒸发结晶,在500℃下煅烧,得到轻质氧化镁;回收热分解产生的氮氧化物气体再生硝酸,常压下再生率达92%以上,实现了红土镍矿中有价组分的高效分离和浸出介质的循环利用。     

镍-钴合金镀层研究进展

镍-钴合金镀层由于其性能优异,被广泛用于零部件的表面装饰与防护。近年来在纳米复合技术发展的基础上,镍-钴合金镀层获得了新的研究和应用。简述了电沉积镍-钴合金的沉积原理,重点综述了镍-钴合金镀层主流镀液体系、镀层性能和镀层的最新进展,并对镍-钴纳米复合镀层的发展进行了展望。     

The solvent extraction of nickel from acidic solutions using synergistic mixtures containing pyridinecarboxylate esters. Part 2: Systems based on alkylsalicylic acids

The synergistic solvent extraction of nickel and cobalt by pyridinecarboxylate esters (2-, 3- or 4-C₅H₄N.CO.OR) in admixture with 3-bromo- or 3-nitro-derivatives of 5-alkylsalicylic acids was studied. Nickel is extracted more strongly than cobalt in all cases and, for systems containing a given pyridinecarboxylate, the pH₅₀ values (pH values for 50% extraction) of both metals decrease in the order: alkylsalicylic acid > bromo-derivative > nitro-derivative. For systems containing a given salicylic acid, the separation between the pH₅₀ values for nickel and cobalt was found to increase in the order: pyridine 2-ester < 4-ester ≈ 3-ester. The extractability of divalent base metals from sulphate solutions by mixtures of isodecyl 3- or 4-pyridinecarboxylate and 3-bromo- or 3-nitro-5-nonylsalicylic acid in Shellsol K decreases through the series: Cu > Ni > Co ≈ Zn > Ca > Mg. In single-stage batch extraction experiments with a simulated leach liquor containing Ni 2·2, Cu 0·5, Ca 0·4 and Mg 5·0 g dm⁻³ (and smaller amounts of other base metals), adjustment of the equilibrium pH value to between 3·3 and 4·0 with magnesium oxide gave extractions of nickel and copper of 97–100%, with co-extractions of calcium and magnesium of <0·5 and <0·1%, respectively. Amongst the metals present in lower concentrations, manganese (2–5%) and lead (5–10%) were extracted only slightly whereas cobalt (40–80%), zinc (15–65%) and iron (100%) were more strongly extracted.     

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.     

含钴废渣硫酸化焙砂浸出液中钴、铁、锰分离研究

对某锌厂含钴废渣硫酸化焙砂浸出液进行了钴与铁、锰分离工艺研究。研究表明 ,焙砂用水浸出时延长时间为 3.5h,可使大量铁以黄铁矾的形式除去 ,再控制溶液 p H3～ 3.5,温度 1 0 0°C,时间 1 h的条件下 ,采用针铁矿法除铁 ,铁的去除率可达 99.5% ,然后控制溶液 p H4～ 4.5,温度1 0 0°C,用 1 0 % ( NH4 ) 2 S2 O8溶液氧化 Mn2 + 为沉淀而除去 ,锰的去除率为 99.8% ,同时还可氧化Fe2 +达到深度除铁的目的 ,铁的总去除率达 99.9%。在此过程中 ,钴的损失率仅为 2 .5% ,取得了令人满意的结果     

硫酸锰深度除杂研究

采用二步法除杂工艺 ,先将硫酸锰中大部分杂质形成硫化物沉淀除去 ,然后再用螯合剂将剩下的少量杂质脱除干净 ,镍的脱除率达 99% ,钴的脱除率达 98%以上 ,锰的损失只有 2 .7% ,除杂后硫酸锰中各重金属杂质含量均在 10mg/kg以下     

Recycling of nickel–metal hydride batteries. I: Dissolution and solvent extraction of metals

Nickel–metal hydride batteries contain valuable metallic components and although they are not considered a hazardous waste, recovery of these materials is necessary from an economic point of view. In this work a hydrometallurgical method for the dissolution and separation of the metals from cylindrical nickel–metal hydride rechargeable batteries was investigated. Hydrochloric acid was employed as the leaching agent to dissolve the metals from the batteries. Dissolution of metals was investigated as a function of acid concentration, leaching time and temperature. Suitable conditions for maximum metal dissolution were 3 h leaching with 4.0 mol dm^?3 hydrochloric acid solutions at 95 °C. Extraction of 98% of nickel, 100% of cobalt and 99% of rare earth elements was achieved under these conditions. Separation of the rare earths from nickel and cobalt was preliminarily investigated by single batch solvent extraction with 25% bis(2‐ethylhexyl)phosphoric acid. Efficient separation via complete extraction of the rare earths was obtained at a pH of approximately 2.5 while leaving nickel and cobalt in the raffinate. A shrinking particle model which can enable, under certain conditions, evaluation of the extent of metal dissolution present in nickel–metal hydride batteries was developed. A proposed electrochemical recovery of nickel and cobalt is also briefly discussed. Copyright © 2004 Society of Chemical Industry     

Separation of Cobalt and Zinc from Manganese,Magnesium, and Calcium using a Synergistic Solvent Extraction System Consisting of Versatic 10 and LIX 63

Abstract

The Boleo leach solution contains large amounts of manganese (45 g/L), magnesium (25 g/L) and small amounts of cobalt (0.2 g/L) and zinc (1 g/L) in sea water. Due to the high manganese concentration, it is very difficult to separate cobalt and zinc from manganese, magnesium, and calcium using conventional solvent-extraction processes, which has led to the development of a synergistic solvent extraction (SSX) system consisting of Versatic 10 and LIX®63. By adding 0.4 M LIX 63 to 0.5 M Versatic 10, large synergistic shifts were obtained for cobalt (max. ΔpH₅₀ 4.24) and zinc (max. ΔpH₅₀ 1.62). After a single contact at pH 4.5, the extraction of cobalt was almost complete and that of zinc 80%. The extraction of manganese was 1.55%, and almost no magnesium and calcium were extracted, indicating excellent separation of cobalt and good separation of zinc from manganese, magnesium, and calcium. The SSX system was further optimized to reduce the co-extraction of manganese with the synthetic Boleo demonstration plant solution. It was found that with 0.33 M Versatic 10 and 0.30 M LIX 63, the SSX system composition approached optimum. After a single contact at pH 5.5, the extractions of cobalt and zinc were 93% and 70%, respectively, while the manganese concentration in the loaded organic solution was only 0.28 g/L. The extraction and stripping kinetics of cobalt and zinc were rapid. The SSX system was tested in two integrated pilot-plant trials with excellent results. Baja Mining has planned to implement the SSX circuit in their future Boleo plant.     

红土镍矿酸浸沉镍废水制备硫酸镁

以元江红土镍矿硫酸溶出液沉镍废水为原料,加入碱式碳酸镁,在室温下利用不同离子水解pH值差异,实现富镁除杂的目的。实验研究了pH值、反应时间、静置时间对废水中离子浓度的影响,确定了较优操作条件为：pH 值 6.5、搅拌通气时间 5 h、静置时间3 h。在此条件下,废水中镁离子的含量提高7.6%,铁、铝、钙、镍杂质离子的去除率分别为99.85%、99.9%、28.57%、35.8%。将此沉镍废水净化液真空浓缩、结晶,分离干燥得七水硫酸镁产品,其质量达到HG/T 2680—95工业七水硫酸镁合格品的要求。     

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.