Organic acid leaching of base metals from copper granulated slag and evaluation of mechanism

A hydrometallurgical method is discussed to selectively extract base metals such as copper, cobalt, nickel and iron from the copper granulated slag (0.53% Cu) at atmospheric pressure. It involves first-stage leaching of slag with organic (citric acid) to selectively recover cobalt, nickel and iron. The residue containing high copper was subjected to second-stage leaching with inorganic (sulphuric) acid. Leaching parameters such as acid concentration, pulp density, temperature and time were optimised to extract metals from the granulated slag. A maximum recovery of 4.47% Cu, 88.3% Co, 95% Ni and 93.8% Fe were obtained in first-stage leaching with 2?N citric acid at room temperature using 10% pulp density (w/v) in 8–9?h. On subjecting the leach residue to the second-stage leaching with 2?M sulphuric acid, 66–72% Cu was recovered in 4?h. The kinetics of the metal leaching from the slag was established by the XRD and SEM–EDAX studies of the residues.     

Reduction-roasting and ferric chloride leaching of copper converter slag for extracting copper,nickel and cobalt values

In a previous investigation the optimum conditions for recovering copper, nickel and cobalt from converter slag through ferric chloride leaching have been described. The study of various parameters revealed that nickel and cobalt recovery could not be improved beyond 24 to 26% respectively from converter slag, though more than 90% of the copper could be extracted. Further attempts were made to bring the metal values completely into solution through reduction-roasting followed by ferric chloride leaching of the slag. The present work comprises a study of various experimental conditions such as concentration of ferric chloride, duration of leaching, duration of reduction-roasting, temperature and nature of reducing agent, to arrive at the optimal recovery of the metal. Under identical experimental conditions a decrease in copper recovery, but an increase in nickel and cobalt recovery has been observed above a roasting temperature of 750°C. The decrease in copper recovery has been attributed to copper ferrite formation which has been confirmed both by leaching experiments with synthetic mixtures and by X-ray diffraction studies with both slag samples and synthetic mixtures. Recovery of nickel has also shown little decline when solid reductants were used above 850°C whereas cobalt recovery remains nearly the same even above 850°C. Under optimum conditions 80% copper, 95% nickel and 80% cobalt could be recovered by reducing the slag at 850°C with 10 wt % furnace oil, followed by leaching with ferric chloride.     

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.     

铜锰渣酸浸及选择性硫化沉淀法回收铜工艺

系统开展了铜锰渣的H₂SO₄浸出及酸浸液Na₂S₂O₃选择性沉铜研究,通过单因素实验,分别探究了2个工艺过程的影响因素。实验结果表明:铜锰渣酸浸的较优条件为:H₂SO₄用量200 g/L,液固体积质量比（mL/g）7∶1,反应温度80 ℃,反应时间2 h,该条件下铜、钴、锌、锰的浸出率分别为99.81%,99.54%,99.07%,24.10%,浸出渣主要物相为MnO₂。酸浸液选择性硫化沉铜的较优条件为Na₂S₂O₃用量倍数2.0,反应时间90 min,反应温度70 ℃,该条件下铜、钴、锌、锰的沉淀率分别为99.99%,0.26%,0.34%,0.29%,沉铜渣主要物相为CuS。经过上述工艺过程,铜的回收率达到99.80%,浸出渣和沉铜渣可直接用于工业生产,沉铜后液可继续分离锌、钴等金属元素。      

硫脲浸取某含金矿石的试验研究

对经过焙烧，且钴、铜、镍、钼、铋等有用元素基本已浸出的某含金多金属矿石浸渣，进行了硫脲浸金试验。试验结果表明。当硫脲用量为8kg／t，浓硫酸用量20L／t，浸出时间为4h，金的浸出率达90％以上。     

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.     

镍精矿加压酸浸新工艺研究

研究了金川镍精矿加压一步全浸镍、钴、铜新工艺,浸出液中和除铜后萃取分离镍钴,镍、钴、铜的浸出率可分别达到99.5%、98%和98%以上。该工艺与硫酸选择性浸出相比具有金属浸出率高、分离彻底、易分别回收等优点。     

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。     

Intensification of sulphation and pressure acid leaching of nickel laterite by microwave radiation

The microwave is a clean and environmentally acceptable energy and various microwave-assisted metal extraction processes have been developed. The novel application of microwave irradiation for sulphation of the nickel laterite ore prior to pressure sulphuric acid leaching has been investigated. Under optimum conditions, about 92% of nickel can be extracted from the ore and above 90% of the iron precipitates as hematite with the residual acid content in the leachate lower than 31 g/L. The microwave sulphation proceeds rapidly and a relatively low leaching temperature and low mass ratio of sulphuric acid to ore can be used in the subsequent pressure leaching to achieve a satisfactory nickel extraction. This may potentially reduce the subsequent heavy capital and operation cost of the pressure acid leaching process.     

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.     

制酸烧渣综合回收铜钴实验

利用沸腾焙烧得到的硫铁矿制酸烧渣为原料,进行了酸浸、铜萃取、除铁、沉钴、尾渣氰化等综合回收铜钴实验研究。实验结果表明,采用沸腾焙烧—酸浸—萃取—除铁沉钴工艺可得到合格的铁精粉;酸浸铜浸出率为70.08%,钴浸出率为60.07%;铜萃取率93.6%,反萃率93.8%;萃余液除铁率大于99.9%,沉钴率大于98.9%。     

废杂铜冶炼渣两段浸出铜锌试验研究

废杂铜冶炼渣经过物理分选出其中部分金属态铜、锌和铁后,依然含有一定量铜、锌、铁和硅的化合物,采用两段湿法浸出处理物理分选后的废杂铜冶炼渣,通过控制浸出初始酸度、浸出时间等措施,Cu、Zn综合浸出率分别达到92.26%和94.83%,第一段浸出液中Fe浓度仅为2.28 mg/L。Cu、Zn与Fe的分离效果好,为后续铜、锌的进一步回收奠定了良好的基础。     

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。     

Pressure leaching of a sulphide copper concentrate with simultaneous regeneration of the leaching agent

An experimental study is presented of leaching of a sulphide copper concentrate with aqueous ferric sulphate under oxygen pressure. The effects of oxygen pressure, sulphuric acid concentration and ferrous iron additions on the copper leaching rate have been determined. Partial pressure of oxygen has been found to govern the rate of copper leaching while the concentration of sulphuric acid only slightly influences this rate. Oxygen enhances the leaching rate mainly by oxidizing ferrous iron to ferric iron — the major leaching agent — and not by direct action on the minerals.Leaching of a sulphide copper concentrate under oxygen pressure with aqueous ferric sulphate leads to a three-fold reduction of both the necessary leaching time and ferric sulphate concentration in the leaching solution over those for conventional leaching with concentrated aqueous ferric sulphate.     

铜转炉渣湿法回收钴研究

通过对铜转炉渣的多元素、物相分析,提出湿法处理工艺。考察物料粒度、初始酸浓度、温度、液固比、浸出时间、搅拌速度、通气速度等因素对铜、钴浸出率的影响。结果表明,采用先筛选粗粒度铜精矿后再硫酸浸出,有利于提高铜回收率,铜的累计回收率达到95%左右,钴与铁的累计回收率达到98%以上。     

从含铜金黄铁矿中综合回收金属铜与金的研究

针对某含有金、银、铜等多种有价元素的黄铁矿，在对其原矿物化性质分析的基础上，通过低温氧化焙烧，烟气制酸，焙砂硫酸浸铜，浸铜渣氰化浸金的工艺对该黄铁矿实现了综合利用.使用上述工艺对含硫45.85%(质量分数)、含铜1.92%(质量分数)、含金1.60 g/t的黄铁矿进行处理，得到铜的浸出率为90.09%，金的浸出率可达70%，氰化渣中铁的含量为63.46%，可作为铁精矿外售.金、铜、铁等有价组分实现了综合回收.      

Activities of CoS and FeS in copper mattes and the behavior of cobalt in copper smelting

The distributions of cobalt and iron between metallic copper and high copper mattes were measured at 1400 and 1500 K. A value of 0.40 ±0.02 was found as the Raoultian activity coefficient of CoS at infinite dilution in the Cu₂S-FeS-CoS mattes. The present activities of FeS in the Cu-saturated Cu₂S-FeS mattes were found to deviate more positively than those reported by Krivsky and Schuhmann at 1623 K, and the positive deviation from the Temkin’s ideality was greater at 1400 K than at 1500 K. Using the activity coefficient of CoS, the partitions of cobalt between copper mattes and fayalitic slags were calculated for various conditions of copper smelting. It was found that cobalt exhibits, in the matte-slag equilibria, chemical properties intermediate between nickel and iron, but much closer to iron than to nickel. The overall recovery of cobalt in blister copper depends on matte grade, and is as low as 3 pct at best. When a high cobalt recovery is desired, therefore, a copper concentrate rich in cobalt must not be processed by conventional pyrometallurgical technology in view of the inevitably high loss to slag. M. NAGAMORI, formerly Associate Professor, Department of Metallurgical Engineering, University of Utah, Salt Lake City, Utah.     

过硫酸铵氧化沉淀法富集净化钴渣中钴的试验研究

某公司生产初期采用α-亚硝基-β-萘酚除钴工艺回收湿法炼锌净化钴渣中的钴,存在药剂消耗量大、钴渣含钴低、生产亏损的问题,后采用过硫酸铵氧化沉淀法富集钴,形成了一种钴的富集倍数高,成本低、流程短、易操作、环保的净化渣回收钴的实用方法。该方法分三个阶段:酸浸阶段包括稀酸选择性浸出和逆流酸性浸出,在较优工艺参数下,钴的浸出率达到95.8%;氧化除铁阶段在较优工艺参数下,滤液Fe含量小于80 mg/L;氧化沉钴阶段可得到含钴20%,锌18%~20%的沉钴渣,将沉钴渣用酸性水洗涤后,可得到含锌小于10%、含钴大于30%的富钴渣,可作为钴精矿销售。该工艺可为从湿法炼锌净化渣综合回收有价金属、富集钴提供参考。     

连续光源火焰原子吸收光谱法测定氧化镍中钴铜锌铁钙镁

采用盐酸溶解样品,选择Co 240.72nm、Cu 324.75nm、Zn 213.86nm、Fe 248.33nm、Ca 422.67nm、Mg 202.58nm作为分析谱线,钴、铜、锌、铁选择3个像素点,钙、镁选择9个像素点,建立了连续光源原子吸收光谱法(CS-AAS)同时测定氧化镍中的钴、铜、锌、铁、钙、镁的方法。实验表明:在100mL测定液中加入2mL 200g/L氯化锶溶液,可消除测定介质(体积分数为2%的盐酸)对待测元素的影响;基体镍对测定的干扰可忽略。在优化的实验条件下,钴、铜、锌、铁、钙、镁的校准曲线相关系数均不低于0.999 0,且其方法检出限在0.002~0.092μg/mL之间。按照实验方法对氧化镍样品中钴、铜、锌、铁、钙、镁分别平行测定11次,钙和镁的测定值在0.1%~0.4%之间,其对应的相对标准偏差(RSD)不大于2%;钴、铜、锌、铁的测定值在0.003%~0.04%之间,其对应的相对标准偏差均小于10%。将实验方法应用于电真空镍光谱标准样品(该标样为氧化镍状态)中上述各元素的测定,结果与认定值基本一致。     

废料中有价金属离子铁、铜、镍的测定及浸出工艺研究

废料中一般含有多种有价金属离子.文中主要是对铁、铜、镍这3种金属离子进行浸出条件分析研究.通过分光光度法得出了铁、铜、镍离子的最佳波长,且在最佳波长处对这3种金属离子可能造成的干扰进行了研究,利用分光光度法测定废料中金属铁、铜、镍的含量.通过对废料中铁、铜、镍离子的浸出条件的研究,设定液固比、浸出温度、浸出时间、加酸量及浸出次数等因素进行实验,从而得出最佳的浸出条件,可使这3种金属离子的浸出率达到最佳.研究结果表明,在液固比为2:1,浸出温度为35 ℃,浸出时间为0.5 h,加入硫酸量为0.5 mL/g废料,在浸出2次的条件下,铁、铜、镍的浸出率分别为97.95 %,99.97 %,98.51 %.