Separation of nickel, cobalt and copper by solvent extraction with P204

Nickel, cobalt and copper were separated by solvent extraction with P204. The experimental results show that [Co(NH 3) 6] 3+ is an inert complex in extraction kinetics, therefore cobalt can be separated from nickel and copper by non equilibrium solvent extraction. Under the conditions of temperature 25?℃, contact time of two phases 10?min, phase ratio 1∶1, aqueous pH 10.10 and concentration of P204 20%, [Co(NH 3) 6] 3+ is hardly extracted by P204, while the percentage extractions of nickel and copper are 79.3% and 93.9% respectively. Nickel and copper are separated by equilibrium solvent extraction with P204. Under the conditions of temperature 25?℃, contact time of two phases 1?min, phase ratio 1∶1, equilibrium pH 4.01 and concentration of P204 20%, the separation factor of copper and nickel is 216.

Process development for the direct solvent extraction of nickel and cobalt from nitrate solution:aluminum,cobalt,and nickel separation using Cyanex 272

A direct solvent extraction（DSX） process for purifying nickel and cobalt from the nitric acid leach solution of nickel laterite ores was conceived and experimentally probed. The proposed process consists of two solvent extraction（SX） steps but with only one extractant - bis（2,4,4-trimethylpentyl）phosphinic acid（Cyanex？ 272） - used in both steps. The first extraction step involved the removal of aluminum and zinc, whereas the second extraction step involved the separation of cobalt along with manganese from nickel. The experimental results showed essentially quantitative removal of aluminum（〉97%） and zinc（〉99%） in a single extraction stage using 20vol% Cyanex 272 at pH 2.1. Some cobalt（32%） and manganese（55%） were co-extracted but were easily scrubbed out completely from the loaded organic phase using dilute sulfuric acid at pH ≤ 1.38. Cobalt and manganese in the first extraction raffinate were extracted completely in four extraction stages at staggered pH values of 4.0, 4.4, 4.5, and 4.0 in the first, second, third, and fourth stages, respectively, using also 20vol% Cyanex 272. A small amount of nickel（up to 6.6%） was co-extracted but was easily scrubbed out completely with dilute sulfuric acid at pH 2.0. A flow diagram showing the input and output conditions and the metals separated under the deduced optimum conditions is presented.

Recovery of nickel,cobalt,copper and zinc in sulphate and chloride solutions using synergistic solvent extraction

A number of synergistic solvent extraction （SSX） systems have been developed to recover nickel, cobalt, zinc and copper from sulphuric and chloride leach solutions by the solvent extraction team of CSIRO, Australia. These in- clude （1） Versatic 10/CLXS0 system for the separation of Ni from Ca in sulphate solutions, （2） Versatic 10/4PC system for the separation of Ni and Co from Mn/Mg/Ca in sulphate solutions, （3） Cyanex 471X/HRJ-4277 system for the separation of Zn from Cd in sulphate solutions, （4） Versatic 10/LIX63 system for the separation of Co from Mn/Mg/Ca in sulphate solutions, （5） Versatic 10/LIX63/TBP system for separation of Ni and Co from Mn/Mg/Ca in sulphate solutions, （6） Versatic 10/LIX63 system for the separation of cobalt from nickel in sulphate solutions by difference in kinetics, （7） Cyanex 272/LIX84 system for the separation of Cu/Fe/Zn from Ni/Co in sulphate solutions, （8） Versatic 10/LIX63fFBP system to recover Cu/Ni from strong chloride solutions, and [9） Versatic 10/LIX63 system to separate Cu from Fe in strong chloride solutions. The synergistic effect on metal separation and efficiency is presented and possible industrial applications are demonstrated. The chemical stability of selected SSX systems is also reported.

Separation of cobalt and nickel by non-equilibrium solvent extraction

The separation of cobalt and nickel in the ammoniacal sulfate solution by non equilibrium solvent extraction with a phosphate (P303) as extractant was studied. In the experiment, the effects of equilibrium pH value in aqueous phase, contact time of the two phases, the air blowing time for feed liquor in the open beaker on percentage extraction of cobalt and nickel and percentage reextraction of nickel from the loaded organic phase with dilute H 2SO 4. etc were studied. The results showed that: Co(Ⅱ) can be oxidized to Co(Ⅲ) ammino complex by adding (NH 4) 2S 2O 8 or blowing air to the aqueous phase, and Co(Ⅲ) ammino complex is a kind of kinetically inert complex. Its extractive speed is very slow, while the nickel′s is much faster than that of cobalt. By controlling the contact time of the two phases, nickel can be separated from cobalt by non equilibrium solvent extraction. Then nickel was reextracted from the loaded organic phase with dilute H 2SO 4.

Solvent Extraction of Nickel and Cobalt from Ammonia-Ammonium Carbonate Solution by Using LIX 84-ICNS

In the present paper, separation of nickel and cobalt in ammonia-ammonium carbonate solution that simulates pregnant leach solution of Caron Process by solvent extraction using LIX 84-ICNS was studied. LIX 84-ICNS is a novel extractant which is still being studied, especially for nickel and cobalt separation in ammonia-ammonium carbonate solution. A series of solvent extraction tests were performed at various equilibrium pH, temperature, extractant concentration, and volume ratio of organic to aqueous solution (O/A ratio). The investigation results show that the highest nickel and cobalt extraction percentages of 99.8% and 90.3% were obtained from the extraction test at equilibrium pH of 8.75, temperature of 55°C, extractant concentration of 40% (v/v) and O/A ratio of 1/1, respectively. Oxidation of cobalt in aqueous solution prior to extraction is needed to minimize co-extraction of cobalt. Co-extracted cobalt can be decreased from 90.3% to 30.3% by mixing 1% (v/v) H2O22 in aqueous solution prior to the extraction stage. It was found that nickel and cobalt extractions by LIX 84-ICNS are endothermic processes with enthalpy changes of +171.03 and +7.64 kJ/mole, respectively. Based on constructed McCabe-Thiele Diagram, nickel extraction level of more than 99.9% can be obtained in 2 stages at O/A ratio of 0.5. The highest stripping percentages of nickel and cobalt of 98.82% and 3.16% respectively were obtained at 200 g/l H2SO4 stripping agent.

Recovery of cobalt and nickel in the presence of magnesium and calcium from sulfate solutions by Versatic 10 and mixtures of Versatic 10 and Cyanex 301

The extraction and stripping characteristics of Versatic 10 and its mixtures with Cyanex 301 were investigated for the recovery of cobalt and nickel from sulfate solutions containing magnesium and calcium. The optimum extraction factors of Versatic 10 were initial pH of 2.5, O/A ratio of 1/3, and saponification rate of 60%. The loaded Versatic 10 was stripped by using 2 mol/L H2SO4 at O/A ratio of 1/1. The optimum volume ratio of Versatic 10 to Cyanex301 was 7/3 in the mixtures, which could effectively reduce the equilibrium pH to 3.50. And the loaded mixtures were stripped by using 2 mol/L H2SO4at O/A ratio of 1/2. The reaction principle of Versatic10 and metal ions is an ion exchange reaction. However, in the extraction reaction of and metal ions, besides the ion exchange reaction, the strong coordination effect between Cyanex 301 and metal ions also exists, which is much weakened in the extraction reaction of the mixtures and metal ions.

Chemical forms of cobalt and nickel extracted by M1,M3 and CaCl_(2)-DTPA

Mehlich 1(M1), mehlich 3(M3) and CaCl 2 DTPA have been used to predict the available micronutrient in soil. However, the forms of micronutrient extractable by these extractants are not known. In the present study, ten soils, collected from five provinces and the capital of China, representing a wide range of chemical and physical properties, were analyzed by sequential extraction to isolate five forms of cobalt and nickel, they are exchangeable, carbonate bound, Fe Mn oxide bound, organically bound and residual forms. The chemical forms extracted by M1, M3 and CaCl 2 DTPA were also investigated. The results show strong correlation between the carbonate bound or organically bound forms of Co or Ni and the amounts of extractable by any of the above three extractants. The main forms extracted by these extractants are carbonate and organically bound forms. The ranking of these three extractants for extraction of Co and Ni are M1>M3=CaCl 2 DTPA and M1=M3>CaCl 2 DTPA, respectively.

Extraction studies of cobalt (Ⅱ) and nickel (Ⅱ) from chloride solution using PC88A

Solvent extraction study of cobalt and nickel were carried out from a chloride solution with a high ratio of Co to Ni using the sodium salt of PC88A as extractant diluted in kerosene. The solution was generated in batches by leaching a tungsten super alloy scraps. The results show that extraction rate of metal ions increases with increase of aqueous phase pH value. The pH0.5 value difference of 1.40 with PC88A indicates the possible separation of cobalt and nickel. Increase of the concentration of the solvent can enhance the percentage extraction of both metal ions. Improvement of temperature is beneficial to extraction separation of cobalt and nickel. Extraction and stripping processes were also studied in a cross-current solvent extraction unit and the results were also given.

PURIFICATION OF COBALT ANOLYTE USING THE NOVEL SOLVENT EXTRACTION SYSTEM

In present research, a novel extractant system (D2EHPA + naphthenic acid + pyridine- ester) was used to purify cobalt anolyte and a simulated industrial production were carried out. This novel extraction system can extract Cu and/or Ni against Co from chloride medium solutions at pH range of 2.5-4.5. About 2g/l nickel and 0.2g/l copper were removed from the cobalt chloride anolyte containing about 100g/l cobalt and 200g/l chloride ions respectively, the raffinate contains nickel and copper less than 0.03g/l and 0.0003g/l respectively and can be used to electrolyze high-purity cobalt. About 5.5t cobalt anolyte was purified in the simulation industrial experiment and kilogram quantities of cobalt of 99.98% purity and about 95% recovery have been produced.

Dialkyl phosphinic acids:Synthesis and applications as extractant for nickel and cobalt separation

Three kinds of dialkylphosphinic acids(DAPAs),i.e.dihexylphophinic acid(DHPA),di-(2,4,4-trimethylpentyl) phosphinic acid(DTMPPA)and didecylphophinic acid(DDPA),were synthesized through free radical addition reaction.The influence of the types of initiator,reation time and reaction temperature on the yield of DAPAs were investigated.The products were characterized by NMR and MS.By using DHPA,DTMPPA and DDPA(10%in kerosene)as extractants,the extraction of Co2 +and Ni2 +in sulphate medium at different equilibrium pH values were measured.The results show that the maximum yield of DHPA, DTMPPA and DDPA can all be achieved at about 130℃under the initiation of di-tert-butyl peroxide(DTBP).All the extraction of cobalt with respect to DHPA,DDPA and DTMPPA precedes that of nickel.The difference in pH1/2 value(defined as the pH at which 50%metal extraction occurs)between cobalt and nickel increases in the following sequence from large to small:DHPA,DDPA and DTMPPA,which indicates that the separation ability for cobalt and nickel ascends from DHPA,DDPA to DTMPPA.

The Property of Alkylthiophosphoric Cobalt and Separation of Co(Ⅱ) and Ni(Ⅱ)

The effect of sulfuric acid solution on the behavior of extracting Co(Ⅱ) and Ni(Ⅱ) with di (2 ethylhexyl) monothiophosphoric acid (D 2EHMTPA) was studied and compared with HEH(EH)P. The reaction equilibrium of extraction can be determined by slope method, equimolar series method and saturation method. The extracting equilibrium constant ( K ex ) and the thermodynamic functions (Δ H 0, Δ S 0, Δ G 0) were evaluated through the determination of the distribution ratio at different temperatures (5～30℃). The solid complex of alklythiophosphate cobalt was synthesized and its thermal stability was studied by TG DTA analysis.

Extraction of valuable metals from low-grade nickeliferous laterite ore by reduction roasting-ammonia leaching method

Nickel and cobalt were extracted from low-grade nickeliferous laterite ore using a reduction roasting-ammonia leaching method.The reduction roasting-ammonia leaching experimental tests were chiefly introduced,by which fine coal was used as a reductant.The results show that the optimum process conditions are confirmed as follows:in reduction roasting process,the mass fraction of reductant in the ore is 10%,roasting time is 120 min,roasting temperature is 1 023-1 073 K;in ammonia leaching process,the liquid-to-solid ratio is 4:1(mL/g),leaching temperature is 313 K,leaching time is 120 min,and concentration ratio of NH3 to CO2 is 90 g/L:60 g/L.Under the optimum conditions,leaching efficiencies of nickel and cobalt are 86.25% and 60.84%,respectively.Therefore,nickel and cobalt can be effectively reclaimed,and the leaching agent can be also recycled at room temperature and normal pressure.

STUDY ON COMPREHENSIVE UTILIZATION OF COBALTIFEROUS SLAG

As a part of comprehensive utilization of concentrate linnaeite.this paper mainly discussed the theoretical bases and technical process conditions of separation of cobalt and nickel by two-section extraction with N,,, and extraction of copper with Lix984

Recovery of Mn^(2+), Co^(2+) and Ni^(2+) from manganese nodules by redox leaching and solvent extraction

The recovery of Mn, Co and Ni from deep-sea manganese nodules was conducted by acid oxidative leaching and solvent extraction. The results indicate that pyrrhotite used during leaching can effectively facilitate the leaching out of manganese, cobalt and nickel. The leaching behaviors of Mn, Ni and Co were determined and the influences of temperature, leaching time and sulphuric acid concentration on leaching rate were also investigated. Co and Ni are precipitated from the leaching liquor by adding sodium sulfide into solution with agitation for 2 h at 50 ℃, and the manganese sulphate is obtained by concentrating the resulting solution. By re-dissolving the precipitates of cobalt and nickel, the separation of cobalt and nickel is performed using di(2-ethylhexyl) phosphoric acid (D2EHPA) for impurities elimination with 8 stages at organic-to-aqueous(O/A) volume ratio of 3:5, and 2- ethylhexyl phosphonic acid mono-2-ethylhexyl ester (known as PC88A or P507) for cobalt extraction with 3 stages counter-current operations at O/A volume ratio of 2:3 followed by their scrubbings and strippings, respectively. The final maximum recovery rates for manganese, cobalt and nickel are 85%, 75% and 78%, respectively.

Solvent Extraction Developments in Southern Africa

The largest solvent-extraction plant in the world at the time, the Nchanga Copper Operation, was in Zambia. The first commercial process using solvent extraction for the refining of the platinum-group metals was in South Africa. More recently, the Southern African region has seen the implementation of solvent extraction for other base metals, precious metals, and specialty metals. These include the world firsts of primary production of zinc at Skorpion Zinc in Namibia and the large-scale refining of gold by Harmony Gold in South Africa. Several other flowsheets that use solvent-extraction technology are currently under commissioning, development, or feasibility study for implementation in this part of the world, including those for the recovery of copper, cobalt, nickel, tantalum, and niobium.

采用Cyanex 301从废旧三元锂电浸出液中萃取分离镍和钴

近年来全球电动汽车销量激增,废旧锂电池的回收愈发迫在眉睫。本文以废旧三元锂电池正极材料的硫酸浸出液为研究对象,采用Cyanex 301选择性分离回收其中的Ni(Ⅱ)和Co(Ⅱ);分别考察了初始pH、萃取相比、萃取时间等因素对各金属萃取率的影响,以及反萃剂HCl浓度、反萃时间、反萃温度等因素对金属反萃率的影响。结果表明:在初始pH=2.0、相比(O/A)为2∶1、Cyanex 301体积分数20%、时间30 min的萃取条件下,经两级逆流萃取,Ni(Ⅱ)、Co(Ⅱ)萃取率分别达97.32%和99.45%。萃取完成后,在最优条件下,通过25℃三级逆流反萃Co(Ⅱ)、80℃两级逆流反萃Ni(Ⅱ),反萃率分别达99.23%和99.08%。最后通过红外光谱和核磁共振氢谱初步证明Cyanex 301萃取Ni(Ⅱ)、Co(Ⅱ)的过程为金属离子与S—H键中的H+发生阳离子交换,且与P=S键形成配位键的过程。

冶金与地球化学过程中Fe-Co-Ni-Cu亲氧性和亲硫性规律

Fe、Co、Ni、Cu在冶金上的提取分离与地球化学成矿在原理上具有高度的相似性,例如岩浆熔离成矿与火法冶金、热液成矿与湿法冶金、风化成矿与湿法冶金、生物地球化学成矿与生物冶金。元素在地球化学迁移和冶金提取过程中体现出的化学性质相似,在地球化学过程中,Fe、Co、Ni、Cu经常伴生成矿,如铁镍矿、镍钴矿、铜钴矿等硫化或氧化类矿物;在冶金过程中,这四个元素则体现出很强的亲氧亲硫化学规律性。利用过渡金属元素Fe、Co、Ni、Cu在成矿中显现出的元素亲和性差异作为相似元素相互分离的理论指导,可以从新的角度理解提取冶金。本文通过分析四种元素的地球化学行为与冶金行为,发现其对氧的亲和性顺序为Fe>Co>Ni>Cu,对硫的亲和性顺序为Fe<Co<Ni<Cu。此结论可为元素选择性硫化、氧化提供理论依据,同时也为金属元素相互分离提供更多可能的研究方法。

Efficient and selective recovery of Ni, Cu, and Co from low-nickel matte via a hydrometallurgical process

Low-nickel matte was intensively characterized, and Ni, Cu, and Co were determined to exist mainly as (Fe,Ni)9S8and FeNi3, Cu5FeS4, and (Fe,Ni)9S8and Fe3O4(in isomorphic form), respectively. The efficient and selective extraction of Ni, Cu, and Co from the low-nickel matte in an (NH4)2S2O8/NH3·H2O solution system was studied. The effects of (NH4)2S2O8and NH3·H2O concentrations, leaching time, and leaching temperature on the metal extraction efficiency were systematically investigated. During the oxidative ammonia leaching process, the metal extraction efficiencies of Ni 81.07%, Cu 93.81%, and Co 71.74% were obtained under the optimal conditions. The relatively low leaching efficiency of Ni was mainly ascribed to NiFe alloy deactivation in ammonia solution. By introducing an acid pre-leaching process into the oxidative ammonia leaching process, we achieved the high extraction efficiencies of 98.03%, 99.13%, and 85.60% for the valuable metals Ni, Cu, and Co, respectively, from the low-nickel matte. © 2017, University of Science and Technology Beijing and Springer-Verlag Berlin Heidelberg.

溶剂萃取法分离提取镍和钴的研究现状及展望

镍和钴作为新能源三元动力电池的原料,工业需求量与日俱增,生产高纯度单一镍和钴产品是工业应用的前提。溶剂萃取法由于具有针对性强、分离系数高、能连续生产和操作简单等优势,已广泛应用工业生产中。本文详细综述有机膦类萃取剂、胺类萃取剂和螯合萃取剂在镍和钴分离提取的应用现状,同时阐述了酸性萃取剂+螯合萃取剂、胺类萃取剂+酸性萃取剂、酸性萃取剂+酸性萃取剂等协同萃取体系的研究,揭示不同体系萃取反应机理,以及工业生产中存在的优劣势。在此基础上,展望了未来溶剂萃取法分离稀土镍和钴的发展方向,为绿色、高效新工艺研发提供借鉴。

新能源战略金属镍钴锂资源清洁提取研究进展

镍钴锂资源提取作为新能源汽车产业链开端环节,决定着其发展命脉。然而我国镍、钴原生矿产资源严重匮乏,且随着硫化镍矿日趋枯竭,国外红土镍矿已成为镍钴主要提取原料。火法高冰镍及湿法高压酸浸作为目前红土镍矿生产电池级硫酸镍的两大主流工艺,各有利弊,两大工艺的并行发展能够为硫酸镍的供应增加更多确定性,进而满足新能源领域对镍钴的庞大需求。我国锂资源丰富但赋存状态不佳,80%锂赋存于盐湖卤水中,长期依赖进口锂矿石。现行盐湖提锂技术中,纳滤法、反渗透、电渗析及吸附法等技术集成耦合所形成的新型提锂工艺,已被多个盐湖的产业化验证,具有广阔的推广应用前景。此外,新型协萃体系TBP/P507-FeCl_(3)的研发,基本解决了原萃取体系存在的问题,有望产业化推广应用。新能源汽车行业的蓬勃发展导致退役电池量呈指数上升,再生金属有望成为原矿金属资源的重要补充,但由于锂电正极材料种类繁多,目前回收系统并不完善。在正极材料的深度回收和处理过程中,浸出体系多采用酸碱体系,易造成二次污染。因此,应进一步研发新型浸出体系,以找到一种温和实用的浸出方法。综上,能源金属提取应以产品为导向,构建从资源到材料到电池应用及回收全生命周期技术体系,以先进技术控制紧缺资源,保障我国新能源行业可持续发展。