Separation of nickel from copper in ammoniacal/ammonium carbonate solution using ACORGA M5640 by selective stripping

Separation of nickel from copper in ammoniacal/ammonium carbonate solution using ACORGA M5640 by selective stripping was carried out. The influence of equilibration time, equilibrium pH and extractant concentration on the extraction of both the metals was studied. It was found that the copper extraction equilibrium was reached in a shorter time than the nickel extraction equilibrium. Nickel extraction decreases above an equilibrium pH of 9.0, while the extraction of copper remains unaffected by the changes in the equilibrium pH range of 7–10. Co-extraction, ammonia scrubbing and the selective stripping of copper and nickel were performed for a solution containing 3 g/l each of copper and nickel and 60 g/l ammonium carbonate. The extraction and the percentage stripping of copper and nickel were almost quantitative.     

The recovery of nickel from high-pressure acid leach solutions using mixed hydroxide product – LIX®84-INS technology

This route for the recovery of nickel from HPAL laterite solutions was successfully demonstrated by the Centaur Mining Cawse Nickel Operation and has been selected by BHPBilliton for their Ravensthorpe Nickel–Yabulu Refinery circuit. The mixed hydroxide route is also well suited to treatment of solutions by other leach processes such as Activox^®.The technology can use an acid strip coupled to nickel electrowinning or an ammonia strip and basic nickel carbonate production. The solvent extraction technology involved in these two circuits is reviewed and compared. The ancillary operations of pregnant leach solution clarification, reagent remediation, reductive stripping of cobalt, zinc and copper transfers are discussed. The treatment of ammoniacal leach solutions containing higher copper concentrations than those normally seen in laterite processing is also addressed.Possible routes for recovery of cobalt and nickel from the solvent extraction circuit are also discussed.     

氨性溶液中铜镍钴的萃取分离

采用PT5050萃取剂，分离和富集镍矿氨液中的铜、镍、钴。采用2级萃取，溶液中铜、镍的萃取率可达99．5％以上，钴不被萃取，经3级低酸选择性反萃镍，镍的反萃率达99％以上，镍反萃液中铜含量小于0．001g/L，满足电镍生产要求。有机相经高酸（180g/L H2SO4)反萃铜，铜反萃液生产电铜或结晶硫酸铜。用硫化钠沉淀萃余液中的钴，钴的沉淀率大于96％，所得到的钴硫精矿含钴大于40％。     

P204/4PC协同萃取分离镍钴与镁钙的研究

采用新型协同萃取剂P204/4PC从含少量镍钴钙的硫酸镁溶液中选择性萃取镍和钴,考察了萃取剂浓度、平衡pH值等因素对萃取分离效果的影响,绘制了萃取、反萃取等温线,并进行了串级模拟萃取?反萃取全流程实验.研究结果表明:P204/4PC协同萃取剂能从硫酸镁溶液中选择性萃取镍钴,实现镍钴与钙镁的高效分离以及镍钴的高倍富集回收...     

Recovery of nickel and cobalt from leach solutions of nickel laterites using a synergistic system consisting of Versatic 10 and Acorga CLX 50

A direct solvent extraction (DSX) process to recover nickel and cobalt from laterite leach solutions is potentially more cost effective compared to the traditional precipitation and re-leaching method. A synergistic solvent extraction (SSX) system consisting of Versatic 10 and Acorga CLX 50 in ShellSol 2046 was studied for DSX nickel and cobalt recovery from a synthetic solution using semi-continuous tests. The effect of pH on the metal distribution profile and metal separation were investigated. It was found that the SSX system can effectively recover nickel and cobalt and separate them from manganese, calcium and magnesium. Over 99% of Ni and Co was extracted using four stages of semi-continuous extraction from the synthetic laterite solution at pH 6.3 and an A/O flowrate ratio of 1:1. More than 80% of the manganese was rejected to the raffinate. The co-extraction of calcium was less than 5% and the co-extraction of magnesium was negligible under these conditions. The co-extracted manganese and calcium were readily scrubbed in three stages semi-continuous scrubbing. The loaded strip liquor with a high concentration of nickel (71.3 g/L Ni) was obtained after two-stage continuous stripping. The final strip solution pH of 3 would be suitable for nickel electrowinning. A conceptual DSX process flowsheet using the SSX system to recover nickel and cobalt from laterite leach solutions after iron removal has been proposed.     

Electrolytic nickel recovery from lithium-ion batteries

Lithium/cobalt/nickel oxide (LiCo_xNi_1−xO₂, 0<x<1) is one of the cathode materials currently used in commercial Li-ion batteries. The direct Ni recovery by electrochemical methods from leach liquor obtained by dissolution of this cathode is not possible because of cobalt anomalous co-deposition.After separating Ni from Co by SX methods, nickel has been recovered by means of both galvanostatic and potentiostatic electrowinning. Operative conditions such as solution pH, temperature, Ni concentration, bath agitation and, in the case of galvanostatic operation, current density have been determined for the selected cathode and anode material.The use of galvanostatic conditions enables a good Ni metal deposit to be obtained, while potentiostatic conditions result in an almost complete depletion of nickel in the electrolyte.     

Comparative study of chelating ion exchange resins for metal recovery from bioleaching of nickel laterite ores

Heterotrophic fungi and their metabolic products have been used in extracting nickel and cobalt from low grade nickel lateritic ores. This study compared the potential of two commercial chelating resins based on iminodiacetate and aminophosphonate functional groups (Purolite S930 and S950) in recovering nickel and cobalt from pregnant bioleaching solutions. The sorption characteristics of these resins were examined using various metal concentrations (from 15 to 2000 mg/L), chelating agents including citric, dl-malic and lactic acids, and solution pH. The solution pH was varied by preparing metal solutions using 0.01 and 0.1 M of organic acids. Metals were recovered from loaded resins using 2 M HNO₃. To interpret the sorption behavior of the resins, the adsorption data were fitted to the Freundlich and Langmuir models. The results showed both nickel and cobalt organic complexes adsorptions were in a good agreement with the two empirical models suggesting that the adsorption mechanisms follow a combination of monolayer and multilayer. The adsorption performance of the aminophosphonate based resin (Purolite S950) was found to exceed that of the Purolite S930. Favourable adsorptions of nickel and cobalt complexes were achieved in weakly acidic solution. Purolite S950 also showed higher selectivity toward nickel and cobalt complexes compared to Purolite S930. The desorption efficiencies from Purolite S950 were about 90% for nickel and from 82% to 98% for cobalt.     

Leaching of limonitic laterite ore by acidic thiosulfate solution

Cobalt is usually recovered as a by-product of copper and nickel processing, and only a small amount of cobalt is derived from laterites although a vast majority of cobalt resources in them. The exploitation of limonitic laterite containing high content of cobalt is becoming increasingly important. The mineralogy of a limonitic laterite ore was characterized by environmental scanning electron microscope (ESEM) and X-ray diffraction (XRD) in this paper. The results show that nickel occurs in goethite mainly, while cobalt is predominantly associated with manganiferous minerals. Thiosulfate is found to be able to selectively leach cobalt from limonitic laterite in the presence of sulfuric acid, and 91% Co, 22% Ni, 10% Fe are leached from an ore containing 0.13% Co, 1.03% Ni within the first 5 min at 90 °C under the conditions of 10 g/L sodium thiosulfate, 8% (w/w) sulfuric acid and 10:1 L/S ratio. The leaching kinetics of Mn and Co by acidic sodium thiosulfate solution can be characterized by the Avrami equation. In acidic solution, thiosulfate readily decomposes into sulfur and sulfur dioxide as intermediary reagents to reduce pyrolusite (MnO₂) and goethite (FeOOH); therefore, nickel and cobalt associated with goethite and pyrolusite respectively are extracted due to reduction dissolution. Furthermore, cobalt is selectively leached over iron and nickel because pyrolusite is preferentially reduced by acidic thiosulfate rather than goethite. The novel process may give an alternative method to selectively recover cobalt as the primary product from limonitic laterites at atmospheric pressure.     

Cyanex 272萃取分离硫酸钴溶液中镍钴的试验研究

采用Cyanex 272萃取剂从硫酸钴溶液中分离去除镍,在有机相组成为25%Cyanex 272+75%航空煤油(用30%NaOH皂化,皂化率75%)、萃原液pH值4.5～5.0、温度25～35 ℃、相比1.5～2条件下,经5级逆流萃取,混合萃取时间5 min,然后用1 mol/L硫酸溶液4级反萃取获得反萃取液,钴直收率达99.86%,Ni去除率达95.20%,钴镍分离效果较好。反萃取后的硫酸钴溶液中杂质含量很低,Co/Ni比达368 95,可以满足生产精制CoSO₄·7H₂O和电钴的要求。     

Studies concerning nickel electrowinning from acidic and alkaline electrolytes

High-purity nickel is mainly produced by electrowinning from sulphate and chloride solutions in the presence of high concentrations of boric acid as a buffer. The generally used pH is in the range 3–4 if Ni concentration in the electrolyte is higher than 10 g/l. Lower Ni concentration, as in the case of either industrial liquid effluents and in situ low grade Ni ore leaching, needs pH values ranging from 10 to 11 in order to hinder the evolution of hydrogen. Ni electrowinning from acidic and alkaline solutions is studied to determine in both cases the best operative conditions. Particularly Ni concentration, additive presence, pH values, temperatures, cathode material, current density and voltage, to be used in the case of low Ni concentration, have been considered to obtain low energy requirements together with pure nickel having a good morphology.     

高效萃取剂AD100从粗硫酸镍溶液中回收铜的研究

采用高效萃取剂AD100从粗硫酸镍溶液中萃取回收金属铜, 考察了初始pH值、相比(A∶O)、萃取剂体积浓度、反应时间等因素对铜回收率的影响。实验结果显示, 在最优的条件下, 即: 初始pH值为2.0, 相比A∶O=3∶1, 萃取剂体积浓度为25%, 萃取时间5 min, 常温下一级萃取即可回收其中94%以上的铜, 铁、镍的萃取率分别低于0.05%和0.01%。对负载有机相进行反萃, 结果显示, 采用2 mol/L的硫酸在相比为1∶1的条件下一级反萃可回收95%的铜。     

应用新一代萃取剂Cyanex272进行钴镍分离的研究

Ｃｙａｎｅｘ２７２是新一代在硫酸盐溶液中分离钴、镍的萃取剂。本文研究了各种因素对Ｃｙａｎｅｘ２７２分离钴、镍的影响,探寻了Ｃｙａｎｅｘ２７２在镍电解净液钴渣处理工艺和高冰镍精炼新工艺中的应用前景。     

Preparation of layered nickel aluminium double hydroxide from waste solution of nickel

The separation of nickel has been carried out from a waste solution containing 3.18 g/L Ni with other impurities such as Fe, Zn, Cu and As. Iron was removed by precipitation and Cu and Zn were removed by solvent extraction using LIX 622N and NaTOPS-99, respectively. After removal of all these impurities nickel was extracted by 1.5 M NaTOPS-99 in two counter-current stages at A:O ratio of 3:1 and the loaded organic was stripped with 30 g/L H₂SO₄ at phase ratio of unity. The strip solution of nickel was treated with Al₂(NO)₃ · 9H₂O for co-precipitation by increasing the pH of solution with 1 M NaOH up to 10. The Ni–Al layered double hydroxide was confirmed through XRD characterization.     

黑镍除钴工艺的研究

黑镍是镍的高价氢氧化物,具有强氧化剂特性,在除钴过程还能深度净化铜、铁、锰、砷等杂质,是镍钴分离的一种好方法。本文研究了黑镍用量、温度、ｐＨ、溶液中钴浓度及黑镍中Ｎｉ￣（３＋）含量对除钴速度的影响。半工业试验和新疆阜康镍冶炼厂的工业实践表明,黑镍除钴工艺应用在硫酸盐体系中是可行的,除钴后溶液作为不溶阳极电积镍的阴极液,生产出的电镍完全符合１号电镍标准。     

Recovery of copper,nickel and cobalt from acidic pressure leaching solutions of low-grade sulfide flotation concentrates

Recovery of copper, nickel and cobalt from the acidic pressure leaching solutions of Jinbaoshan (YN Province, PRC) low-grade sulfide flotation concentrates was investigated. The proposed technique includes four major steps: (1) the acidity adjustment of the acidic pressure leaching solutions; (2) solvent extraction (SX) separation of copper by organic reagent XD5640, and then stripped from the loaded organic phase by H₂SO₄ solution for copper recovery; then (3) iron in raffinates after copper extracting is selectively removed by high-temperature hydrolysis precipitation in an autoclave; and lastly (4) nickel and cobalt are selectively precipitated by Na₂S from the final solutions after removing iron. The experimental results for treating 1 L acidic leaching solutions per batch by this new technique were reported, and some evaluation and further comparisons with previous investigations were also carried out. It was reported that the total percent recovery of Cu could reach 95% or more, and that of Ni and Co were all more than 99%. In the processing, the percent removal of impurities, such as Fe, Mg and Ca, were all also near to 99%.     

铜阳极泥氯化浸金液连续萃铜试验

针对铜阳极泥氯化浸金液含铜高造成稀贵金属置换困难且损失量大的问题,采用Lix984萃取分离铜,进行萃取槽连续试验,考察铜萃取率变化,分析存在的问题并探讨解决方案。试验发现采用Lix984从含铜10～20g/L和Cl-～200g/L的氯化浸金液中分离和回收铜,技术上可行。在萃取混合时间3min、萃取相比(O/A)2/1、反萃水相为180～260g/L硫酸条件下,经过4级萃取、2级洗涤和2级反萃,铜直收率可达99%以上。金、银、钯、铅、镍等不被萃取,仅有少量夹带,可洗涤回收。萃取过程发生界面污物累积和乳化,主要与料液含固量高、金属离子水解、相比和搅拌速度不当、萃取剂降解等因素有关,可通过精滤、过渡槽调pH值、实时监控流量和转速、定期补充萃取剂和清除第三相等措施,实现萃取稳定运行。     

形貌控制合成纤维状氧化亚镍粉末新型前驱体

以可溶性镍盐和草酸或草酸铵为原料, 利用氨为配位剂, 通过配位沉淀法制备了纤维状氧化亚镍粉新型前驱体, 并采用XRD、红外光谱(IR)和扫描电镜(SEM) 研究了前驱体粉末的物相、成分与形貌, 系统考察配位沉淀条件包括溶液pH值、反应温度、反应物浓度和表面活性剂对前驱体粉末形貌、粒度和成分的影响。结果表明: Ni(Ⅱ)-C₂O4^2--NH₃-NH₄⁺-H₂O反应体系中, 在溶液pH值为8.2～8.8, 温度为60～70 ℃, Ni²⁺浓度为0.5～0.8 mol/L, 表面活性剂聚乙烯吡咯烷酮(PVP)用量为0.1%～0.5%条件下得到的新型前驱体为草酸镍氨复盐, 其形貌为纤维状; 氨与镍离子配合并生成草酸镍氨复盐是纤维状形貌形成的内在机制。通过在空气中热分解该种前驱体即可得到比表面积为5.944 m²/g、轴径比大于50的纤维状氧化亚镍粉末。     

用N235从大洋多金属结核萃铜余液中萃取钴

研究了用N235从大洋多金属结核熔炼-锈蚀-萃取工艺中所产出的萃铜余液中萃取分离钴的方法。实验结果表明, N235萃取钴效果明显, 负载有机相中的钴能被稀酸反萃完全。采用N235萃取和稀酸反萃方法可以把Co(Ⅱ)、Ni(Ⅱ)分离开。从含钴0.85 g/L的料液中, 按相比V_O/V_A= 1/2, 经四级逆流萃取, 二级反萃可将钴富集到15.20 g/L, 萃余液中含钴0.0055 g/L, 萃余液中Ni/Co高达1 838, 反萃液中Co/Ni =1 520, 产品质量符合优质工业氯化钴质量要求, 钴镍萃取分离效果甚佳, 钴的回收率大于98%。     

Cobalt and zinc recovery from copper sulphate solution by solvent extraction

It has been demonstrated in earlier works that zinc as an impurity can be effectively removed from cobalt sulphate solutions (Zn/Co < 1) by solvent extraction with D2EHPA. Some process residues from copper plants contain both cobalt and zinc as valuable metals, which have to be separately extracted for their recovery. Leaching of such residues leads to solutions with higher Zn/Co ratios (Zn/Co > 10). Again, solvent extraction with D2EHPA has been successfully used to separate cobalt and zinc into their respective solutions, which could further be treated by appropriate techniques for the production of these metals.The method mainly consists of selective copper extraction with LIX 984, iron removal by precipitation with CaCO₃, simultaneous cobalt and zinc extraction with D2EHPA followed by their separation by selective stripping with sulphuric acid of different concentrations. The use of a specific cobalt extractant is not necessary. More than 95% copper has been recovered from the pregnant solution typically containing 1.0 g/l Co²⁺, 2.0 g/l Cu²⁺, 12.60 g/l Zn²⁺ and 8.4 g/l Fe³⁺. The cobalt and zinc recoveries were on an average of 90% each in their respective individual solutions.