Recovery of Co（Ⅱ） and Ni（ Ⅱ） from hydrochloric acid solution of alloy scrap

A hydrometallurgical process was developed for recovery of nickel and cobalt from the hydrochloric acid leaching solution of alloy scraps. The process consists of five maj or unit operations： 1） leaching with 6 mol/L hydrochloric acid under the L/S ratio of 10：1 at 95 ℃ for 3 h; 2） copper replacement by iron scraps under pH value of 2.0 at 80 ℃, and stirring for 1 h, 3） removal of iron and chromium by chemical precipitation： iron removal under pH value of 2.0 at 90 ℃ by dropwise addition of sodium chlorate and 18% sodium carbonate solution, then chromium removal under pH value of 4.0 at 70 ℃ by addition of nickel carbonate solution, stirred by air flow for 2 h; 4） selective separation of cobalt from nickel by extraction using 30% trialkyl amine＋50% kerosene （volume fraction） and tri-n-butylphosphate （TBP） as a phase modifier with the O/A ratio of 2：1, and stripping of cobalt with 0.01 mol/L HCl; 5） crystallization of nickel chloride and electrodeposition of cobalt. It is found that the nickel recovery of 95% and the cobalt recovery of approximately 60% with purity over 99.9% are obtained by this process.     

Pressure nitric acid leaching of alkali-pretreated low-grade limonitic laterite

The pressure nitric acid leaching of alkali-pretreated low-grade limonitic laterite, as well as removing impurity Al(III) and preparing intermediate product of nickel/cobalt sulphide from leaching liquor were investigated. After pretreatment, iron exists in the form of amorphous iron oxides, while nickel is adsorbed on the surface of iron oxides in the form of nickel oxide. The preferable pressure leaching conditions are determined as follows: leaching temperature of 458 K, leaching duration of 60 min, initial acidity of nitric acid of 1.90 mol L-1and liquid to solid ratio of 3:1(volume to mass ratio). Under these conditions, the leaching efficiencies of Ni, Co and Al are 95 %, 88 % and 55 %, respectively, and that of Fe is less than 1 %. The loss rates of Ni and Co are 1.8 % and1.5 %, respectively, during the step of removing impurity Al(III). The sulphide precipitation process produces the interim production of nickel/cobalt sulphides, recovering greater than 99 % of Ni and Co in the purified solution.The iron-rich([60 %) pressure leaching residue with low Cr, S can be further reclaimed as the raw materials for iron making.     

Preparation of LiNi1/3Co1/3Mn1/3O2 cathode materials from spent Li-ion batteries

A recycling process including separation of electrode materials by ultrasonic treatment, acid leaching, Fe-removing, precipitation of cobalt, nickel, manganese and lithium has been applied successfully to recycle spent lithium-ion batteries and to synthesize LiNi1/3Co1/3Mn1/3O2. When ultrasonic treatment with 2-nitroso-4-methylphenol（NMP） at 40 ℃ for 15 min, the electrode materials are separated completely. Above 99% of Co, Ni, Mn and Li, 95% of Fe in the separated electrodes are acid-leached in the optimized conditions of 2 mol/L H2SO4, 1：2 H2O2：H2SO4 （molar ratio）, 70 ℃, 1：10 initial S：L ratio, and l h. 99.5% of Fe and less than 1% of Co, Ni, Mn in the leaching solution can be removed in the conditions of initial pH value 2.0-2.5 adjusted by adding 18% Na2CO3, 90 ℃ and stirring time 3 h. After adjusted to be equal by adding NiSO4, COSO4 and MnSO4 solution, 97.1% of Ni, Co, Mn in the Fe-removing surplus leaching solution can be recovered as Ni1/3Co1/3Mn1/3（OH）2. 94.5% of Li in the surplus filtrate after the deposition of Co, Ni and Mn can be recovered as LiECO3. The LiNi1/3Co1/3Mnl/3O2, prepared from the recovered compounds, is found to have good characteristics of the layered structure and elecrtochemical performance.     

Phase transformation in reductive roasting of laterite ore with microwave heating

Selective reduction of laterite ores followed by acid leaching is a promising method to recover nickel and cobalt metal, leaving leaching residue as a suitable iron resource. The phase transformation in reduction process with microwave heating was investigated by XRD and the reduction degree of iron was analyzed by chemical method. The results show that the laterite samples mixed with active carbon couple well with microwave and the temperature can reach approximate 1000 ℃ in 6.5 min. The reduction degree of iron is controlled by both the reductive agent content and the microwave heating time, and the reduction follows Fe2O3→Fe3O4→FeO→Fe sequence. Sulphuric acid leaching test reveals that the recoveries of nickel and iron increase with the iron reduction degree. By properly controlling the reduction degree of iron at 60% around, the nickel recovery can reach about 90% and iron recovery is less than 30%.     

Selectively leaching Cu(Ⅱ）and Ni(Ⅱ) from acid mine drainage sludge by using ethylenediamine-ammonium sulfate

A method based on controlling the complexation-precipitation equilibrium of metal ions was proposed to selectively recover nickel and copper from hydroxide sludge formed by lime neutralization of acid mine drainage (AMD),Ethylenediamine(EDA) and ammonium sulfate were chosen as com,plex reagent and precipitating reagent,respectively,to dissolve target metal hydroxides from sludge and limit useless metal ions in the pregnant solution.Results from both synthetic and natural samples show the excellent selectivity for the target metals(copper and nickel) against Fe(Ⅲ）,Ca(Ⅱ) and Mg(Ⅱ）,99% recovery of Cu(Ⅱ） and Ni(Ⅱ）and shorter leaching time can be reached by this process,and the resultant solution can be used for direct electrowinning.The optimum operating conditions are:pH=9-11,ρ(EDA)=40g/L,ammonium sulfate 50g/L,leaching time 5h(for natural sample) and 2.5h(for synthetic sludge),liquid to solid ratio being 4 with mechanical stirring at room temperature.     

Synthesis of LiNi1/3CO1/3Mn1/3O2 cathode material via oxalate precursor

Using oxalic acid and stoichiometrically mixed solution of NiCl2, CoCl2, and MnCl2 as starting materials, the triple oxalate precursor of nickel, cobalt, and manganese was synthesized by liquid-phase co-precipitation method. And then the LiNi1/3Co1/3Mn1/3O2 cathode materials for Li-ion battery were prepared from the precursor and LiOH-H2O by solid-state reaction. The precursor and LiNi1/3Co1/3Mn1/3O2 were characterized by chemical analysis, XRD, EDX, SEM and TG-DTA. The results show that the composition of precursor is Ni1/3Co1/3Mn1/3C2O4·2H2O. The product LiNi1/3Co1/3Mn1/3O2, in which nickel, cobalt and manganese are uniformly distributed, is well crystallized with a-NaFeO2 layered structure. Sintering temperature has a remarkable influence on the electrochemical performance of obtained samples. LiNi1/3Co1/3Mn1/3O2 synthesized at 900 ℃ has the best electrochemical properties. At 0.1C rate, its first specific discharge capacity is 159.7 mA·h/g in the voltage range of 2.75-4.30 V and 196.9 mA·h/g in the voltage range of 2.75-4.50 V; at 2C rate, its specific discharge capacity is 121.8 mA·h/g and still 119.7 mA·h/g after 40 cycles. The capacity retention ratio is 98.27%.     

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.     

A novel process of extraction and separation of RE and Mn from Panxi rare earth mud

A novel process to extract and separate rare earth (RE) and manganese (Mn) from Panxi rare earth mud was devdoped. The process involves roasting the mud at 480℃ with NH4Cl as chlorinating agent, and leaching the calcine with hot water to obtain a rare earth chloride solution. After the solution was further purified, HD(DIBM)P (P507) was applied as extractant to separate RE and Mn. By seven stages of fractional extraction, the RECl3 and MnCl2 solutionswith 99.8% purity were obtained. Finally, the purified RECI3 and MnClz solution were precipitated by NH4HCO3 to obtain a crystal RE2(CO3)3 and MnCO3 products respectively.     

Solvent extraction of molybdenum from acidic leach solution of Ni–Mo ore

A P204(D2EHPA) diluted with sulfonated kerosene was used for the selective extraction of molybdenum from an acidic Ni–Mo ore leach solution that was reduced using sodium thiosulfate. The results indicate that P204(D2EHPA) is an effective extractant for the extraction of molybdenum. The extraction of Mo is more than 90 % at pH of 0.5, contact time of 10 min, and organic-toaqueous phase(O/A) ratio of 1:1 with 10 vol% P204(D2EHPA). Molybdenum in the loaded organic phase can be effectively stripped with ammonium acid carbonate solution, and the stripping of molybdenum with 60 g L-1 ammonium acid carbonate solution is 94.67 % at O/A ratio of 2:1 and contact time of 10 min.     

Experiment Research on the Enrichment of Precious Metals from Nickel-copper-iron Matte

According to the chemical and phase composition of the nickel-copper-iron matte containing precious metals and the progress in enrichment of precious metals from the nickel-copper-iron matte containing precious metals at home and abroad, this paper put forward the process route of enrichment of precious metals and selectively leaching of base metals from the nickel-copper-iron matte by sulfuric acid and sodium hypochlorite. The effects of particle size, leaching temperature, leaching time, amount of sulfuric acid and sodium hypochlorite on the leaching rate of nickel, cobalt, copper and iron are mainly discussed. The results show that raw material particle size has significantly effects on the leaching rate of base metals, high leaching rate of base metals and enrichment of precious metals are obtained with the suitable particle size. Through the experiments, the reasonable experiment parameters and conditions were determined as fellows: particle size of-200 to +250 mesh, leaching temperature 95℃ , leaching time 5 h, sulfuric acid concentration 30%, adding amount of sodium hypochlorite 3 times of matte weight. Under these experiment parameters and conditions, the leaching rate of nickel, cobalt, copper and iron were 97.39%, 96.24%, 98.30% and 99.01%, respectively. The content of nickel, cobalt, copper, iron in the leaching residues was 8.15%, 0.23%, 1.40% and 0.24%, respectively. The content of Pt, Pd, Au, Ag and Rh in the leaching residues was 247 g/t, 521 g/t, 112 g/t, 494 g/t and 24 g/t, respectively. The content of Pt, Pd, Au, Ag and Rh in the leaching solution was <0.0005 g/L, 0.0023 g/L, 0.0007 g/L, <0.0005 g/L and 0.00017 g/L, respectively. This process has advantages as follows: a small investment, simple technology, high enrichment efficiency.     

Process for cobalt separation and recovery in the presence of nickel from sulphate solutions by Cyanex 272

The present paper deals with the extraction of cobalt from a solution containing cobalt and nickel in a sulphate medium similar to the leach liquor obtained by the dilute sulphuric acid pressure leaching of the Pacific Ocean nodules matte followed by copper extraction. The commercial extractant Cyanex 272 (bis (2, 4, 4-trimethylpentyl) phosphinic acid) is used for this purpose. The leach liquor used for the present study contains Co =1.78 g/L and Ni=16.78 g/L. Before cobalt extraction, impurities, such as copper and iron, are removed from the leach liquor by the precipitation method. Increasing the concentration of Cyanex 272 increased the extraction percentage of cobalt due to the increase of equilibrium pH. Cobalt extraction efficiency of >99.9 % is achieved with 0.20 M Cyanex 272 in two counter-current stages at an aqueous: organic (A:O) phase ratio of 1.5∶1. Complete stripping of cobalt from the loaded organic containing 2.73 g/L Co was carried out at pH 1.4 by a synthetic cobalt spent electrolyte in two stages at an A:O ratio of 1∶2. The enrichment of cobalt during extraction and stripping operations was about 3.5 times. A complete process flowsheet for the separation and recovery of cobalt is presented.     

镍红土矿高压酸浸过程的金属元素浸出行为

以镍、钴的提取为目的,研究褐铁矿型镍红土矿高压酸浸过程中各金属元素的浸出行为,探讨硫酸加入量、浸出温度、浸出时间及液固比对各金属元素浸出率的影响.实验结果表明,在优化条件下Ni、Co、Mn和Mg的浸出率分别达到97%、96%、93%和95%以上,则Fe的浸出率小于1%.对高压浸出渣的分析表明,渣中的铁和硫主要分别以赤铁...     

Selective recovery of cobalt,nickel and lithium from sulfate leachate of cathode scrap of Li-ion batteries using liquid-liquid extraction

This paper focuses on the extractive separation and selective recovery of cobalt, nickel and lithium from the sulfate leachate of cathode scrap generated during manufacture of lithium ion batteries (LIBs). The conditions for extraction, scrubbing and stripping of cobalt from nickel and lithium are optimized with an aqueous feed containing 25.1 g·dm^?3 cobalt, 2.54 g·dm^?3 nickel and 6.2 g·dm^?3 lithium using Na-PC-88A. 99.8% Co is extracted with 60% Na-0.56 mol·dm^?3 PC-88A in two counter-current stages at an O/A phase ratio of 3/1 and an equilibrium pH of 4.5. The “crowding effect” shown for the first time provides effective scrubbing of impurities (Ni and Li) with 2.0 g·dm^?3 CoSO₄ solution. The McCabe-Thiele diagram predicts the scrubbing of 99.9% Ni and 99.9% Li at an equilibrium pH of 4.75 and O/A of 2/1 in two stages. High purity (99.9%) cobalt sulfate along with Ni and Li from the leach liquor of cathode scrap is recovered by solvent extraction. The proposed process ensures complete recycling of the waste of the manufacturing process of LIBs.     

Synthesis and characterization of LiNi0.45Co0.10Mn0.45O2 cathode for lithium ion batteries

1INTRODUCTIONAdvanced rechargeable lithium ion batteriesare attractive for use in consumer electronic andelectric vehicle(EV)application because of a fa-vorable combination of voltage,energy density,cycling performance,and have been developed rap-idly worldwide during the past decade[1,2].LiCoO2has been widely used as a cathode material in com-mercial lithiumion battery because it is reasonableeasy to synthesize and shows a stable discharge ca-pacity[3].But due to its high cost and toxic…     

Recovery of valuable metals from anode material of hydrogen-nickel battery

Simultaneous recovery of rare earth, nickel and cobalt resources from the anode material of hydrogen-nickel battery was performed through a hydrometallurgical process. Most of rare earth elements are separated from nickel and cobalt in the form of sulfates when the anode material is firstly leached with sulfuric acid. Then, the precipitated rare earth sulfates are dissolved with sodium hydroxide to form rare earth hydroxides. The rare earth element, zinc and manganese ions in the lixivium are also separated from nickel and cobalt by using PC-88A extractant system, and the organic phase loaded rare earth is stripped with hydrochloric acid. By neutralizing the stripping solution with rare earth hydroxide, the rare earth chloride is obtained. Under the suitable leaching conditions of sulfuric acid 3 mol/L, leaching time 4 h and temperature 95 ℃, 94.5% of rare earth in the anode material is transformed into the sulfate precipitates, and the leaching ratios of nickel and cobalt can approach 99.5%. When the pH value of the extractive system is controlled in the range of 3.0-3.5, the rare earth elements in the lixivium can be extracted completely into the organic phase, and the stripping recovery of the rare earth can reach 98% in the extraction stage. The total recoveries of rare earth, nickel and cobalt are 98.9%, 98.4% and 98.5%, respectively.     

Study of spent battery material leaching process

The recovery of Ni, Co and Mn from spent battery material is very important to environment protection, utilization of resources and cost reduction of the material. The dissolution rates of Ni, Co and Mn with hydrochloric acid as leachant are all over 95% under the optimal conditions of initial hydrochloric acid of 6 mol/L, particle size of 120 μm for the exhausted scraps, molar ratio of H2O2 to MeS of 2, leaching temperature about 60 ℃, ratio of liquid to solid of 8, and leaching time of 2 h. The NixCoyMnz precursor for cathode material prepared from the purified leaching solution, can meet the demand of precursor by pure chemicals. The process is economic and feasible for base metals from spent battery material.     

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

1 Introduction Since the first commercial process using di-2-ethyl hexyl phosphoric acid (D2EHPA) was developed by RITCEY et al[1], the organophosphorus extractants have been proved to be primary solvents for separation cobalt from nickel in acidic media…