Dissolution of lateritic nickel ore using ascorbic acid as synergistic reagent in sulphuric acid solution

The dissolution of nickel and cobalt from Caldag lateritic nickel ore using the combination of sulphuric and ascorbic acids was investigated. The use of other organic acids, namely citric, maleic and stearic acids, as synergistic reagents was studied for comparison. The results revealed that the use of ascorbic and citric acids markedly improved the dissolution of cobalt compared to the other two organic acids that only showed slight synergistic effect on the leaching rate. In terms of nickel dissolution, ascorbic acid is the most effective synergist, followed by citric, maleic and stearic acids in descending order. Under the most optimized conditions found in this study, i.e., using 1 mol/L of sulphuric acid with the presence of 4 g/L of ascorbic acid at 80 °C and solid-to-liquid ratio of 1/10, more than 99% and 98% leaching rates of cobalt and nickel, respectively, can be achieved within 4 h of leaching. In addition, the leaching performance is relatively insensitive to the change of ascorbic acid concentration from 2 to 4 g/L which is highly desirable from operational perspective.     

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...     

Pressure leaching of metals from waste printed circuit boards using sulfuric acid

Printed circuit boards (PCBs) are essential components of electronic equipments which contain various metallic values. This paper reports a hydrometallurgical recycling process for waste PCBs, which consists of the novel pretreatment consisting of organic swelling of PCBs followed by sulfuric acid leaching of metals from waste PCBs. To recycle the waste PCBs, experiments were carried out for the recovery of copper from the crushed and organic swelled materials of waste PCBs using sulfuric acid leaching in presence of hydrogen peroxide under atmospheric and pressure condition. The leaching of PCBs at 90°C, pulp density 100 g/L under atmospheric condition, using 6M sulfuric acid resulted in the dissolution of a minor amount of copper due to the presence of plastic coating on the surface of metallic layers. On the other hand, when the liberated metal sheets from organic swelled PCBs were treated with dilute sulfuric acid of concentration 2M along with hydrogen peroxide in an autoclave under oxygen atmosphere, the percentage recovery of copper was found to increase from 59.63% to 97.01% with an increase in hydrogen peroxide concentration from 5 to 15% (v/v) keeping constant pulp density 30 g/L.     

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.     

助剂作用下不同浸取方法从电解锰渣中回收锰

以8-羟基奎宁、原磺酸酯、十六烷基三甲基溴化铵、磷酸三丁酯、柠檬酸为浸取助剂,对普通浸取法和超声浸取法从锰渣中回收锰进行考查,对助剂类型和用量、固液比、浸取温度、浸取时间和酸渣比对锰浸出率的影响进行了探讨.结果表明:以质量百分比浓度为1%的柠檬酸为浸取助剂,当固体的质量与液体体积比为1:4(g/mE)、酸的体积与锰渣质量比为0.3:1(mL/g)、在60℃温度下浸取120 min,锰渣中锰浸出率为55.6%.相同条件下,超声浸取15 min,锰浸出率为55.4%.超声助剂浸取法锰浸出率是普通无助剂浸取法的2.69倍,是无助剂超声浸取法的1.5倍.对于相同的浸出率,超声助剂浸取法的浸取时间只有普通浸取法的1/8.     

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%.     

常温铁系磷化液

通过正交试验优化后确定了一种常温铁系磷化液的最佳配方:11 ml/L磷酸(85%),15.5 g/L磷酸氢二铵,2.5 g/L硝酸镍,2 g/L柠檬酸,2.5 g/L钼酸铵,1 g/L氟化钠,1 ml/L OP乳化剂.试验结果表明,该磷化液具有组成简单,成本低,污染小,沉渣少,且膜致密均匀,耐腐蚀性强等特点.     

The activox® process: Growing significance in the nickel industry

Metal-market analysts project a global nickel supply gap which will be filled by further high-pressure acid leach treatment of laterite ores and the commercialization of hydrometallurgical refineries to recover nickel from sulfide ores. The Activox® process is one such hydrometallurgical technology developed to recover a range of base and precious metals from sulfide ores and concentrates. The combination of ultrafine grinding and oxidative leaching extracted and enabled the recovery of 96.2% nickel, 88.3% cobalt, and 82.9% copper in the 310 kg/h Tati Hydrometallurgical Demonstration Plant.     

水钴矿中选择性提取铜和钴的新工艺

针对某水钴矿的特点,采取还原酸浸旋流电积新工艺选择性提取其中的铜和钴。系统考察初始硫酸浓度、温度、时间、Na2SO3用量、液固比等因素的影响,确定浸出最佳条件如下:初始硫酸浓度为75g/L,Na2SO3用量为7%,液固比L/S=4 mg/L,温度为70℃,时间为0.5 h。对浸出液进行了旋流电积提取铜和钴的探索实验研究,得到纯度分别为99.95%、99.97%的电积铜、钴产品,铜、钴的直收率分别达到98.23%和94.54%。     

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.     

还原酸浸法从低品位水钴矿中提取铜和钴

以Na2SO3为还原剂从水钴矿还原酸浸液中提取铜和钴,研究了还原剂种类及用量、浸出温度、硫酸浓度等因素对水钴矿还原酸浸过程中有价金属铜和钴浸出率的影响。结果表明,Na2SO3是较适宜的还原剂;在还原剂用量为水钴矿原矿质量的10%、硫酸浓度为3 mol/L、浸出温度为60℃、液固比为2-1、浸出时间为60 min的条件下,铜和钴的浸出率分别达99.06%和98.87%。并提出了"M5640萃铜→黄钠铁矾法除铁→碳酸钠除铝→氟化钠除钙、镁→蒸发结晶得钴产品"的后续分离净化流程,能有望应用于水钴矿及类似物料中有价金属的提取与分离的工业生产。     

加压浸出脱除钴白合金中金属铜和钴的研究

阐述了采用加压浸出方法对金属铜和钴进行有效脱除。实验结果表明：加压浸出过程的较佳反应条件为反应温度150℃、硫酸浓度30 g/L、反应压力1.5 MPa、反应时间6 h、液固比6：1。在此反应条件下,金属Cu、Co的浸出效率分别达到了90％和88％。     

湿法炼锌净化渣酸浸的动力学

对湿法炼锌净化渣的浸出动力学进行了研究,并探讨了硫酸浓度、反应温度、粒度等对钴、锌浸出率的影响规律。从动力学的角度分析了整个浸出过程,得到优化条件：液固比50：1(mL/g),硫酸浓度100 g/L,反应温度70°C,粒度75~80μm,反应时间20 min。在此优化条件下钴的浸出率为99.8%,锌的浸出率为91.97%。结果表明：在硫酸体系中钴的浸出符合不生成固体产物层的“未反应收缩核”模型。通过 Arrhenius 经验公式求得钴和锌表观反应活化能分别为11.693 kJ/mol和6.6894 kJ/mol,这表明浸出过程受边界层扩散控制。     

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.     

Presentation of the U.R. Evans Award for 1983 to Professor G. C. Wood

Abstract

Prominent examples of inhibitors recommended to protect metallic materials, especially ferrous metals and alloys, from corrosion in hydrochloric, sulphuric, nitric, hydrofluoric, phosphoric, sulphamic, citric, acetic, hydroxyacetic or formic acid or ammonium bifluoride, during acid pickling, scale removal, acid cleaning or oil and gas well acidizing, are discussed with respect to the individual problems connected with the technical applications of these various kinds of acid treatment. The structures of organic inhibitors are given including N-containing compounds (amines, Mannich bases, alkynoxymethylamines, ammonium compounds heteroaromatics, oximes, nitriles, nitro compounds), acetylenic alcohols, S-containing compounds (mercaptans, thioethers, sulphonium compounds, sulphoxides, thioureas, thiocyanates, heteroaromatics, etc.) and complexones.     

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.     

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.     

Recycling of WC-Co hardmetal sludge by a new hydrometallurgical route

A hydrometallurgical process based on aqua regia treatment of WC-Co hardmetal sludge was developed to simultaneously extract cobalt in solution and forming tungstic acid as residue in a single step. The parameters such as aqua regia concentration, temperature and time of reaction, and pulp density were optimized to process the sludge containing 60.9 wt.% W, 5.99 wt.% Co, 3.38 wt.% Fe and 12.64 wt.% C as the major components. Almost complete leaching of cobalt was achieved with 100 vol.% of aqua regia at 100 °C temperature, 60 min reaction time and 400 g/L pulp density. Complete conversion of tungsten carbide of the sludge to tungstic acid was observed at and below the pulp density of 150 g/L under this condition. The progress of reaction and conversion of tungsten carbide to tunstic acid (H₂WO₄) were investigated by XRD phase identification of the residues under different conditions. The tungstic acid produced from the acid treatment was purified by dissolving tungsten in 11.20 mol/L of ammonia solution at 60 °C while rejecting insoluble metallic impurities as a residue. Tungsten from the ammoniacal solution was recovered by evaporation-crystallization process as high purity (99.97%) ammonium paratunstate (APT, (NH₄)₁₀·H₂W₁₂O₄₂·4H₂O) with low levels of impurities.     

Study of decomposing carbonyl slag

1 Introduction Carbonyl slag is a kind of solid from the material with nickel by carbonylation. It usually contains Cu, Ni, Co, Fe, S, As, Sb, Au, Ag and platinum metals, and holds great recovery value. At present, with the development of the technology o…     

硫酸铵焙烧法浸出镍磁黄铁矿中有价金属

将镍磁黄铁矿与(NH4)2SO4混合后在高温下焙烧,考察(NH4)2SO4用量、浸出温度、浸出时间和稀硫酸浸出液的pH值对焙烧产物中金属元素浸出率的影响,并在氨水-(NH4)2SO4混合溶液中浸出焙烧产物。结果表明:在不同情况下,Ni和Cu的浸出率较高,Mg和Fe的浸出率较低;氨性溶液有利于Ni和Cu的浸出,总氨浓度为7 mol/L时,Ni和Cu的浸出率分别为89.56%和79.35%;低pH值的稀硫酸溶液有利于Mg和Fe的浸出,pH值为0.5时,Mg和Fe的浸出率分别为61.39%和62.56%。由扫描电镜-能谱分析和XRD分析可知,矿样中Ni和Cu大部分被浸出;由于焙烧产物中部分Mg和Fe以铁酸钙和硅酸镁等形态存在,Mg和Fe的浸出率较低。