Pressure leaching of copper converter slag using dilute sulphuric acid for the extraction of cobalt, nickel and copper values

In our earlier studies [1–4], conditions were optimized for leaching converter slag with ferric chloride/dilute sulphuric acid for the recovery of cobalt, nickel and copper. By using both leachants most of the copper, nickel and cobalt values could be solubilized. Subsequent treatment of the leach liquors for separation and recovery of metals was difficult due to the presence of large quantities of iron in relation to other metal concentrations. In the present work, an attempt has been made to develop a process based on pressure leaching of the slag with dilute sulphuric acid in which iron contamination could be minimized by oxidation and hydrolysis. Various parameters including leaching time, pulp density, particle size, concentration of acid and oxygen partial pressure were studied to optimize the solubility of metal values. Under optimum conditions about 90% copper and more than 95% each of nickel and cobalt could be extracted with only 0.8% extraction of iron.     

Recovery of cobalt,nickel and copper from converter slag through roasting with ammonium sulphate and sulphuric acid

Roasting of copper converter slag containing 4.03% copper, 1.98% nickel and 0.48% cobalt with ammonium sulphate open to atmosphere has been carried out in order to achieve sulphation of copper, nickel and cobalt followed by leaching of the metal values as soluble sulphates with water. The effect of parameters such as temperature (200–600°C), time (15–120 min), and amount of ammonium sulphate (0.5–2.5 times stoichiometric) has been studied. Under atmospheric conditions, using 2.5 times the stoichiometric requirement of ammonium sulphate, the recovery of copper, nickel and cobalt was found to be 85%, 81% and 85%, respectively. Similar studies were carried out with sulphuric acid. The influence of experimental variables such as the amount of sulphuric acid (0.25–2 times stoichiometric), roasting temperature (100–300°C) and time (15–120 min) has been studied. Under optimum conditions, i.e., at 150°C and a roasting time of 60 min with the stoichiometric amount of sulphuric acid, recoveries of copper, nickel and cobalt were 95, 90 and 99%, respectively, along with a contamination of 60–80% iron. Removal of most of the iron from the leach liquors has been effected with ammonia liquor and lime as precipitants. A two-stage roasting operation using sulphuric acid, first at 150°C and then at 650°C, has resulted in bringing the iron content down to about 3% in the sulphation product without much affecting the recovery of other metal values.     

高冰镍浸出渣冶金过程多金属走向行为探究

高冰镍浸出渣是镍湿法冶金过程的重要中间产物,含有铜、镍、钴和金、银、铂、钯等有价金属,具有重要的综合回收价值。探究高冰镍浸出渣冶金过程多金属的走向行为对于提高金属综合回收率、优化系统物料平衡和推动工艺技术升级具有重要意义。基于新疆阜康冶炼厂高冰镍浸出渣的典型冶金工艺,结合文献调研和工业生产实践,阐释高冰镍浸出渣中主要金属铜、镍、钴、铁和贵金属金、银、铂、钯的迁移走向,揭示各金属形态变化历程,分析各金属在渣相和液相的分配行为,为工艺设计和优化提供支撑。     

复杂高硅钴白合金脱硅预处理—常压浸出新工艺

开展复杂高硅钴白合金浸出回收有价金属铜、钴的新工艺研究。基于浸出热力学分析,提出分段浸出钴、铜以实现两者分离。经碱焙烧脱硅预处理,钴白合金结构得以去稳定化,新物相的生成也有利于钴、铁在第一段高效溶出。经试验确定了第一段常压浸出较优工艺条件,钴、铁浸出率均可达99%以上,而几乎全部铜都保留在浸出渣中,钴、铜分离效果理想,该浸出工艺具有良好的稳定性。经第二段三级逆流连续常压浸出,可取得比较理想的铜浸出结果。     

重金属加压浸出技术现状及展望

加压浸出作为一种高效的湿法冶金手段,迄今为止已在铜、锌、镍、钴等重金属行业,以及铀、钼、黄金和铂族等稀贵金属行业得到推广应用。总结了重有色金属铜、铅、锌、镍、钴行业和冶炼过程副产物加压浸出技术研究和工业化应用现状,包括复杂硫化铜矿、铜钴矿、硫化砷渣、黑铜泥、铜阳极泥、白烟尘和铜钴冶炼转炉渣加压浸出,复杂硫化锌矿、锌浸出渣、赤铁矿除铁、镓锗富集物、铜渣等加压浸出,硫化镍矿、红土镍矿、白合金、铜渣和钴冰铜加压浸出等。最后,对加压浸出技术在重有色金属行业未来发展趋势进行了展望。     

从氨溶液中萃取镍的试验研究

用某镍矿粗制的氢氧化镍中,铁、钙、镁、硅、铜、锌、钴等杂质含量较高,进一步氨浸后,镍、铜、锌、钴等生成金属-氨络合物进入溶液,用氨性萃取剂萃取、硫酸反萃取,可将镍与其他杂质分离,获得满足电积要求的镍溶液.     

Bioleaching of Rare Metals from Manganese Nodules by Thiobacillus Ferrooxidans

Manganese nodules, which constitute a potential future resource of rare metals, are composed mainly of oxides of manganese and iron, with various metals such as copper, nickel, and cobalt. Although physical and chemical processes have been developed for extracting the rare metals from manganese nodules, another possible process is the leaching of metals by microbial means.

This paper describes leaching of raw manganese nodules by sulfurous acid and sulfuric acid which are biologically produced by oxidation of elemental sulfur by Thiobacillus ferrooxidans. The bioleaching behavior of each metal from nodules was measured at 30°C and pH 2 in a well-mixed batch reactor. The metal content of the nodules used in this work was 0.29% Cu, 0.49% Ni, 0.27% Co, 16% Fe and 17% Mn by weights. For both the microbial system and the control culture containing no T.ferrooxidans, copper and nickel exhibited close to 100% leaching in two weeks and less than 5% for iron and manganese. On the other hand, leaching of cobalt was markedly accelerated in the microbial system reaching 50% in two weeks compared with the sterile control. The bioleaching rate of cobalt was enhanced as the initial sulfur-liquid loading ratio became higher, but is was practically independent of the nodule size which was less than 330 mesh. Moreover, there was an optimal relation between the bioleaching rate and the initial cell concentration, and the addition of T.ferrooxidans cells in excess of the optimal concentration resulted in a decrease in the leaching rate of cobalt.     

从废弃炉渣中分离回收钴、镍

用酸（硫酸＋少量硝酸）浸出废弃炉渣,其中的Cu、Ni浸出率达99％以上,Co浸出率为87％。浸出液用铁粉置换法分离铜、黄钠铁矾法除铁、NaF法除钙镁、P204深度除杂、P507分离镍钴,杂质去除率达99．5％以上,Ni、Co回收率均超过94％。     

高铁硫化矿选择性浸出铁的研究

将镍钴火法冶炼转炉渣进行还原硫化,制备成富含镍钴铜的高含铁硫化矿,并采用加压选择性浸出其中的铁。对铁的浸出行为进行了研究。结果表明,随着铜浸出率从98%降到-42%,铁浸出率从3%升到43%左右,选择性浸出后液含铁越来越高,而且以二价铁居多,这是造成高铁硫化矿难以进行加压选浸的主要原因。     

Recovery of metal values from copper converter and smelter slags by ferric chloride leaching

A study of the recovery of copper, nickel and cobalt from copper converter and smelter slags by leaching with ferric chloride is reported. The converter slag from Ghatsila, India contained 4.03% copper, 1.99% nickel and 0.48% cobalt and the smelter slag contained 1.76% copper, 0.23% nickel and 0.19% cobalt. Various parameters including the effect of stirring, leaching time, leaching temperature, concentration of ferric chloride, solid-liquid ratio and particle size, on the extraction of copper, nickel and cobalt have been studied. 92% copper, 28% nickel and 24% cobalt could be extracted from converter slag under optimum conditions, whereas 54% copper, 71% nickel and 44% cobalt could be extracted from smelter slag.     

钴冰镍常压浸出工艺研究

以镍转炉渣还原硫化熔炼得到的钴冰镍为原料,在常压下于硫酸体系中进行浸出,考察了硫酸浓度、液固比、浸出时间及浸出温度对钴冰镍中有价成分浸出率的影响。结果表明,液固比和硫酸浓度对钴、镍、铁的浸出率影响较大。当硫酸浓度为1.6mol/L、液固比5、浸出时间2.5h、浸出温度85℃时,铁浸出率达到69%,镍、钴浸出率分别控制在1%和5%以内,取得了很好的选择性浸出效果。     

从氧化钴矿石中提取钴的试验研究

研究了从氧化钴矿石中回收钴.通过两段浸出,浸出渣中钴质量分数小于0.5%,钴浸出率达99%.通过黄钾铁钒法除铁,氟化钠法除钙、镁,亚硫酸钠法除铜,P204串级萃取法进一步去除杂质Fe、Ca、Mg、Cu、Zn、Mn、Pb、As等,P507萃取分离钴镍,最后通过沉淀得草酸钴产品,产品纯度符合要求.     

Recovery of germanium and other valuable metals from zinc plant residues

The main purpose of this study was to characterize and to extract germanium from the copper cake of Çinkur Zinc Plant. The physical, chemical and mineralogical characterization of the ground copper cake sample obtained from Çinkur showed that it was 84% below 147 μm containing 700 ppm germanium. The copper cake also contained 15.33% Cu, 15.63% Zn, 1.66% Cd, 1.33% Ni, 0.64% Co, 0.35% Fe, 2.62% Pb, 12.6% As, 0.18% Sb and 3.42% SiO₂. The mineralogical analysis indicated the complex nature of the copper cake which was mainly composed of metallic and oxidized phases containing copper, arsenic, zinc, cadmium, etc. The sulfuric acid leaching experiments were performed under the laboratory conditions. The optimum collective extraction of germanium and other valuable metals was obtained at a temperature range 60 to 85 °C for a leaching duration of 1 h with sulfuric acid concentration of 150 gpl and using a solid–liquid ratio 1/8 g/cc. Under these conditions, the recovery of germanium was 92.7% while the other metals were leached almost completely. The optimum selective leaching conditions of germanium was determined as half an hour leach duration, 1/8 g/cc solid–liquid ratio, 100 gpl sulfuric acid concentration and a temperature range 40 to 60 °C. Under these conditions the leach recovery of germanium was 78%. The dissolution's of other metals like cobalt, nickel, iron, copper, cadmium and arsenic were almost low. So, germanium would be separated more selectively at the following precipitation by tannin stage.     

羰化渣处理工艺的研究

介绍了国外现有的羰化渣处理工艺，提出了一种新的羰化渣处理工艺流程，此流程的特点在于：它采用低压低酸浸出，最终实现了羰化渣中镍、铜、钴与贵金属的有效分离及贵金属的富集。     

对我国电镍生产工艺的分析与改进研究

对我国电镍生产主要工艺存在的问题进行分析,并提出工艺改进方案。在现有不溶阳极电积精炼工艺基础上,采用常压浸出渣添加焙砂加压选择性浸出固定硫、浸铜后渣电炉还原熔炼、产出的铜镍锍用返液及镍和铜电积的阳极液分段浸出等措施解决现有工艺的内在矛盾和缺陷,提高对原料成分波动的适应性,分阶段集中和提高各有价金属的回收率。     

Studies on Processing of an Alnico Scrap

This paper presents the results of research and development work on processing of alnico scrap, a secondary resource of nickel and cobalt, generated during the manufacturing of alnico magnets. The scrap contains 8–10% nickel, 10–12% cobalt, 32–50% of iron, 8–10% aluminium, 2% copper and remaining silica. Various processes such as acid leaching, aqueous chlorine leaching, salt roasting and cupric chloride leaching were studied in detail. Of these cupric chloride leaching was found to be most effective with respect to recovery and purity. It has been possible to obtain pure nickel and cobalt salts by cupric chloride leaching of the scrap, solvent extraction and precipitation of the salts. The overall recovery by the above process was almost 99%.     

富钴结壳湿法冶金工艺中硫化渣的加压浸出

富钴结壳活化硫酸浸出液经过中和除铁、硫化沉淀后得到的渣采用加压浸出工艺处理,考察了温度、压力、酸度、液固比等因素对加压浸出过程的影响,确定了加压浸出条件,此时镍、钴的浸出率大于99.8%,铜的浸出率大于98%,加压浸出得到的镍、钴、铜混合溶液可进一步萃取分离得到纯净的金属溶液。     

A new method for recovering valuable metals from low-grade nickeliferous oxide ores

A new method, the concentrated sulfuric acid acidolysis and water leaching (SAWL) of nickeliferous oxide ores, is proposed and the optimal conditions for recovery of nickel, cobalt and copper from a low-grade Chinese nickeliferous oxide ore are presented. A series of experiments were conducted which examined the effect of acid charge, acid curing temperature and acid curing time. Recoveries of up to 95%, 83% and 95% for Ni, Cu and Co, respectively were obtained with only the sulfuric acid at ambient temperature and atmospheric pressure. Comparing the percolation leaching with agitation leaching showed that percolation leaching was capable of extracting the valuable metals with water. The SAWL method was scaled to three-stages counter-current leaching tests using 1 kg of ore. The results indicate greater than 90% extraction for nickel and cobalt.     

Sulphuric acid leaching of cobalt-bearing manganese wad

Manganese wad from the Mt. Tabor region of Queensland, Australia, contains in excess of 1% cobalt with lesser amounts of nickel and copper. As such, it presents a significant cobalt resource, particularly in terms of Australia's cobalt requirements. Because of the remote location and the lack of infrastructural facilities, potential processing routes need to be kept as simple as possible. There are many similarities between terrestrial manganese wads and deep-sea manganese nodules, and so routes developed for the processing of the latter should be applicable to the wad. Of these routes, sulphuric acid leaching at atmospheric pressure and ambient temperature appears to have considerable potential.This paper describes the results obtained with sulphuric acid leaching using the pug, agitated tank and column techniques. Even with excess acid, dissolution of the cobalt, copper and nickel from the wad was found to be extremely slow, with reaction times of weeks and months required for more than 50% dissolution. No conditions could be found where selective dissolution of cobalt, copper and nickel over manganese occurred. Comparative tests were carried out with Pacific Ocean deep-sea manganese nodules.Because of the low leaching rate found with sulphuric acid at atmospheric pressure and ambient temperature, commercial exploitation of the Mt. Tabor wad with this leachant under these conditions seems unlikely. Previously reported work indicates that a better approach will be to use sulphur dioxide as the leachant, even though this is a considerably more expensive leachant.     

Extraction of nickel,cobalt and other metals [Cu,Zn, Fe(III)] with a commercial β-diketone extractant

The extraction of nickel, cobalt, copper and zinc from ammoniacal solutions of ammonium carbonate or ammonium sulphate by solutions of Hostarex DK-16 in kerosene has been investigated as a function of phase contact time, aqueous-phase pH and organicphase reagent concentration. Besides copper, Hostarex DK-16 also partially extracts iron (III) from moderately acidic solutions whereas nickel, cobalt(II), copper and zinc are extracted from neutral or ammoniacal ammonium sulphate and ammonium carbonate solutions. Extraction decreases in the following order of metals: Cu > Co > Ni > Zn. Cobalt(III) is not extracted, but the complex of cobalt(II) with Hostarex DK-16 is slowly oxidized to a cobalt(III) complex which cannot be stripped even when 10 N sulphuric acid is used. Absorption spectra for cobalt complexes with Hostarex DK-16 (purified by preparative thin-layer chromatography) in benzene also suggest oxidation of cobalt(II) to cobalt(III) in the organic phase. Nickel, cobalt(II), zinc and copper can be stripped easily from organic solution with dilute solutions of sulphuric acid. Hostarex DK-16 extracts iron very slowly, nickel moderately rapidly and copper, cobalt(II) and zinc rapidly. Slope analysis and extraction isotherms suggest that the complexes CuR₂, NiR₂ ·HR and CoR₂·HR are present in the organic phase. Nickel can easily be separated from cobalt by extraction with Hosterex DK-16 after oxidation of cobalt in aqueous ammoniacal solution by hydrogen peroxide; however, LIX 64N seems to be a more promising extractant owing to the higher extraction of nickel under analogous conditions and the poorer extraction of zinc in comparison with Hostarex DK-16.