Pressure acid leaching of a Chinese laterite ore containing mainly maghemite and magnetite

The high pressure acid extraction of nickel and cobalt from a Chinese laterite containing mainly maghemite and magnetite was studied. X-ray diffraction (XRD) and scanning electron microscopy/X-ray energy dispersive spectroscopy (SEM/EDS) were employed to characterize the residues. The factors influencing the dissolution of maghemite and magnetite, nickel and cobalt extractions and iron precipitation were investigated. The results show that after 75 min at 270 °C with an acid/ore ratio of 0.55, maghemite and magnetite completely dissolved, liberating 98% Ni and 88% Co into the leach liquor. EDS analysis reveals that some nickel may be associated with the amorphous silica and/or basic ferric sulfate, resulting in a minor loss of nickel. The presence of a cobalt-containing phase in the residues, believed to be ringwoodite, is mainly responsible for the incomplete extraction of cobalt. Both maghemite and magnetite dissolved gradually with the increase in temperature from 200 to 270 °C. Maghemite dissolved more slowly than magnetite at 270 °C which also produced ferrous sulfate in the leach liquor and increased the total iron extraction. Increasing temperature and/or agitation accelerated the hydrolysis of ferric sulfate. The leaching of maghemite and magnetite corresponds to a dissolution-precipitation mechanism. In both high and low acidic environments, the precipitation of ferric sulfate proceeds through the initial formation of basic ferric sulfate and its conversion to hematite. The extent of conversion depends largely upon residual acidity and reaction time.     

印尼某褐铁矿型红土镍矿原矿微观结构的探讨

研究对象印尼某红土镍矿为褐铁矿型红土镍矿,具有品位低、成分复杂等特点。为了查明印尼某红土镍矿的微观结构特征从而达到合理且最大程度地回收矿物中Ni、Fe组分,实验利用偏光显微镜、扫描电镜(SEM)、X射线衍射(XRD)和矿物自动解理系统(MLA)等多种测试分析手段对原矿的物相组成、主要矿物的嵌布特征等展开研究。结果表明:100~900℃的温度梯度范围内,该褐铁矿型红土镍矿先后经历了针铁矿脱羟基转变成赤铁矿和铁橄榄石相的形成过程。该印尼红土镍矿中金属矿物主要由针铁矿、铬铁矿、赤铁矿等氧化物组成,脉石矿物主要由石英、铁橄榄石和绿泥石等硅酸盐组成。针铁矿是Ni、Cr、Co、Al的主要赋存矿物,且都是以类质同象的形式代替Fe元素形成的固溶体矿物,该矿物也是后期Ni、Fe分离的目的矿物。     

Comparative leaching of minerals by sulphuric acid in a Chinese ferruginous nickel laterite ore

The Yuanjiang nickel laterite ore containing mainly maghemite, goethite and lizardite was leached by sulphuric acid at atmospheric pressure and the residues were characterized using X-ray diffraction and scanning electron microscopy/X-ray energy dispersive spectroscopy. The relationship was discussed between the extraction of nickel, cobalt, iron, magnesium, aluminum, and the dissolution behaviour of the laterite minerals; as well as the extent of congruency of nickel, cobalt and iron extraction. The results show that the solubility of the laterite minerals in sulphuric acid decreases in the following order: lizardite > goethite > maghemite > magnetite ≈ hematite > chromite ≈ ringwoodite. Lizardite dissolved rapidly in 0.6 mol/L sulphuric acid at 60 °C whilst goethite dissolved completely in 2.5 mol/L sulphuric acid at 80 °C. The dissolution of the primary mineral maghemite was slow, but increased with increasing acid concentration and leaching temperature. Magnetite dissolved more slowly than maghemite; and hematite was only dissolved in > 6.2 mol/L sulphuric acid at 105 °C. Chromite and ringwoodite were not dissolved. The leaching behaviour of the laterite minerals may be explained by the bond strength differences of Me–O and the substitution of metal cations in the mineral structure.     

The leaching of nickeliferous laterite with ferric chloride

Several experiments were conducted to investigate the extraction of nickel from nickeliferous laterite by ferric chloride solutions as a function of pulp density, solution composition, and temperature. Solubility relationships for goethite and nickel laterite in aqueous solution were reviewed in terms of leaching rates and reaction mechanisms. Generally, the amount of nickel extracted increased with temperature, the amount of “free acid,” and ferric chloride concentration; however, the amount was inhibited by ferrous chloride. In this investigation, as much as 96 pct of the available nickel was extracted by ferric chloride solution. Nickel extraction was found to be more dependent on ferric chloride concentration than on the concentration of hydrochloric acid. Mechanistically, nickel extraction occurred by the formation of an intermediate ferric chloride complex, which was then hydrolyzed to hematite.     

红土矿还原焙砂常压酸浸液用SO2/O2氧化除铁的研究

在实验室条件下采用SO2和O2混合气体为氧化剂,开展了从预还原焙烧红土矿常压酸浸液中氧化、除铁的研究.模拟浸出液中Fe2+的质量浓度为10.2 g/L,实验温度分别为60、70、80和90℃.氧化后的Fe(Ⅲ)基本以针铁矿的形式沉淀除去,沉淀过程中加入碱式碳酸镁为中和剂以维持溶液pH值恒定.氧化、沉淀除铁的pH值控制范围为1.7至3.2.实验结果表明,SO2和O2混合气体可加速Fe2+的氧化,且SO2的优化配比取决于混合气体的流量.在优化配比情况下,混合气体中SO2的利用率在97%左右.SO2含量超过最优配比时,过量的SO2则会被溶液中的Fe3+氧化.除铁沉淀渣中的镍含量(质量分数)不超过0.05%,镍仅有少量损失于除铁渣中.     

红土镍矿富集镍和铁的焙烧、氢气还原和磁选分离

对印尼红土镍矿的基础特性进行了系统的研究,发现矿石主要由蛇纹石和辉石组成,其中Ni元素主要以类质同象的形式取代Mg元素存在于蛇纹石中.在此基础上分别进行了红土镍矿焙烧、氢气还原、磁选分离镍和铁的一系列实验研究.红土镍矿与碳酸盐添加剂进行混合焙烧实现了Ni和Fe氧化物的释放;对焙烧产物进行氢气还原,还原产物中Ni和Fe元素以金属形态存在,Fe金属化率最高超过80%,远大于原矿还原产物中Fe的金属化率(4%-8%),且随着温度升高,Ni元素易与Fe结合生成Fe-Ni;磁选所得产物中Ni和TFe品位分别达到3%和20%,Fe和Ni的回收率分别达到80%和90%,初步实现Ni和Fe的富集.      

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％。     

从废旧三元锂离子电池中回收有价金属的新工艺研究

废旧三元锂离子电池经过放电、焙烧、破碎、筛分等预处理方法分离出电池活性物质、集流体与钢壳,再采用H2SO4-Na2SO3对废电池粉料（活性物质）进行浸出,浸出液调节pH至4.5,过滤以除去铁和铝,滤液再调pH至11左右,将锂和镍钴锰分离,得到的锂液经过浓缩后加入Na2CO3得到工业级的LiCO3,在镍钴锰富集物中加入氨水将锰和镍钴分离,最后使用P507分离镍和钴,在相比O/A=1,平衡pH=4.5,有机相组成为25% P507 75%溶剂油,经二级逆流萃取后钴的萃取率为99.3%。使用200 g/L硫酸为反萃剂,相比为5时,钴的回收率达99.21%。反萃液使用草酸铵沉钴,萃余液中的镍采用氢氧化钠沉淀,整个工艺流程中钴的回收率为91.82%,镍的回收率为91.12%。     

Selective separation of nickel from cobalt in ammoniacal solutions by emulsion type liquid membranes using 8-hydroxyquinoline (8-HQ) as mobile carrier

The selective separation and concentration of nickel from ammoniacal solutions containing nickel and cobalt by an emulsion liquid membrane (ELM) technique using 8-hydroxyquinoline (8-HQ) as carrier has been examined. The emulsion liquid membrane consists of a diluent (kerosene), a surfactant (ECA 4360J), a carrier (8-HQ), and a stripping solution (0.025 M EDTA solution, buffered at pH 4.0). Cobalt (II) in the 6 M ammonia feed solution was oxidised to cobalt (III) by adding H₂O₂ and the pH adjusted to 10 with hydrochloric acid (HCl). The important variables were found to be membrane composition, ammonia concentration, diluent type, surfactant concentration, extractant concentration, EDTA concentration in the stripping solution, pH of the feed and the stripping solutions, phase ratio, and treatment ratio. It was possible to selectively extract 96.5 to 99.0% of nickel from a mixture of nickel and cobalt.     

印尼某红土矿硫酸加压浸出矿物组成变化研究

印尼苏拉威西岛La-paopao矿区红土镍矿储量约7326万吨,含镍约为1.25％,以此红土镍矿为对象,系统分析了矿样中主要矿物的种类、赋存状态及产出特征.结果 表明:矿样含Fe (40.15％),Ni(1.42％),Co(0.15％),Mg(0.37％),SiO2(6.92％)(质量分数),是典型的褐铁型红土镍矿;组...     

Recovery of nickel and cobalt from laterite leach solutions using direct solvent extraction: Part 2: Semi- and fully-continuous tests

In Part 1 of this paper, two synergistic solvent extraction systems consisting of Versatic 10/LIX63/TBP and Versatic 10/4PC were assessed in batch tests for the separation and purification of nickel and cobalt from synthetic laterite leach solution after iron removal. In Part 2, semi- and fully-continuous tests are reported for the Versatic 10/LIX63/TBP system, with conditions optimised for separating nickel and cobalt from manganese, magnesium and calcium.Semi-continuous extraction tests were conducted using the synergistic organic system consisting of 0.50 M Versatic 10, 0.45 M LIX63 and 1.0 M TBP in Shellsol D70. With a pH profile of 5.5/6.1/6.5 for the three stages EX1/EX2/EX3 at 40 °C, the nickel and cobalt extractions were 99.9% with only 5 mg/L nickel and < 1 mg/L cobalt left in the raffinate. With two stages of scrubbing and a pH profile of 5.4/5.0 at 40 °C, about 2 mg/L manganese and less than 1 mg/L magnesium and calcium were left in the scrubbed organic solution. With two stripping stages and an O/A ratio of 10 at 40 °C using 50 g/L H₂SO₄ as strip solution, the stripping efficiencies of nickel and cobalt were over 95%.A fully-continuous pilot plant was operated for 280 h. With an O/A ratio of about 2 and a pH profile of 5.5/5.8/6.0/6.3 for the four stages EX1/EX2/EX3/EX4 at 40 °C, both nickel and cobalt were almost completely extracted. The nickel and cobalt concentration in the raffinate was lower than detection limit of 0.2 mg/L. The manganese, magnesium and calcium concentrations in the loaded organic solution were 34, 8 and 1 mg/L, respectively. Using a pH profile of 5.4/5.0 for SC1/SC2 at an O/A ratio of 10 and 40 °C, the manganese scrubbing efficiency was over 96% and the concentrations of manganese and magnesium in the scrubbed organic solution were < 5 mg/L and that of calcium 1 mg/L. Using three strip stages and a strip solution containing 50 g/L H₂SO₄ and 55 g/L Ni at an O/A ratio of 10 and 40 °C, over 98% Ni and 99% Co were stripped with only 64 mg/L Ni in the stripped organic solution. The nickel concentration in the loaded strip liquor was 86 g/L, giving a ΔNi of 31 g/L. The loaded strip liquor contained less than 1 g/L acid.     

A comparative study on extraction of Fe(III) from chloride leach liquor using TBP, Cyanex 921 and Cyanex 923

A comparative study on extraction of Fe(III) from the HCl leach liquor of low grade iron ore tailings has been carried out using Tri-n-butyl phosphate (TBP), Cyanex 921 and Cyanex 923 in distilled kerosene. The percentage extraction of iron increased with increasing HCl and extractant concentrations. The extracted species in each case was found to be HFeCl₄·S. The extraction isotherms for the above extractants indicated quantitative extraction of Fe(III) in 3-stages at O:A ratio of 3:2 with TBP, and in 2-stages at O:A ratio of 1:1 with Cyanex 921 and Cyanex 923. The stripping studies of the loaded organic phases were carried out with 0.4 M HCl. The stripping isotherms indicated 2-stages at O:A ratio of 5:2 for TBP, and 3-stages at O:A ratio of 2:3 for Cyanex 921 and Cyanex 923. From the extraction studies, the extraction efficiency of the extractants for Fe(III) was in the order TBP < Cyanex 921 < Cyanex 923. Although Cyanex 923 was found to be the best extractant, the percentage stripping of Fe from the loaded Cyanex 923 was the least. The stripping of Cyanex 923 was 94.9%, but with TBP and Cyanex 921, it was 99.8% and > 99.9%, respectively.     

Awaruite (Ni3Fe) as a nickel resource—leaching with ammoniacal–ammonium solution containing citrate and thiosulfate

A method was developed for extraction of nickel from ultramafic rocks containing awaruite, an alloy of nickel and iron (nominally Ni₃Fe). The leaching solution contained ammonia, ammonium, citrate and thiosulfate at moderately alkaline pH. Leaching studies were carried out on synthetic Ni₃Fe, josephinite (a naturally occurring material consisting mainly of awaruite from Oregon, USA) and serpentinite containing low levels of awaruite from British Columbia, Canada. In addition to citrate, several other carboxylic acid ligands were also found to be suitable for this process.     

Novel reagents for iron and sulphur control in medium temperature leaching of sulphide concentrates

Hydrometallurgical leaching of sulphide concentrates of copper and nickel at medium temperature (150°C) produces residues that contain sulphur and iron-bearing minerals and phases. During leaching, and depending on various process parameters, iron may be precipitated as hematite, goethite, jarosite or other oxyhydroxides, which may be more or less crystalline. Hematite is the favoured iron precipitate, because it is the most environmentally stable and does not ad/absorb as much copper, nickel or other solution constituents during precipitation. However, the low solubility of iron during the medium temperature processing of sulphide ores can favour the formation of poorly crystalline, nano-scale iron oxide/oxyhydroxide phases. In some cases, these phases have been positively identified as the metastable ferrihydrite, which transforms into iron oxides such as goethite, hematite and magnetite over time. A better understanding of what may help drive this transformation during leaching would ultimately result in lower valuable metal losses and more stable leach residues. Higher acid concentrations result in increased copper extractions and favour the formation of hematite during concentrate leaching, rather than other metastable phases. Furthermore, commercially available water displacement formula ‘WD40®’ and other novel reagent(s) affect Fe precipitation and sulphur chemistry, leading to very different process outcomes such as improved extractions and larger, more easily separated, sulphur particles.     

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.     

Selective separation of copper and nickel by solvent extraction using LIX 984N

Selective separation of copper and nickel from ammoniacal/ammonium carbonate medium was carried out by using LIX 984N diluted with deodourised kerosene. The study of the influence of equilibration time, equilibrium pH, extractant concentration and selective stripping of copper and nickel has been optimized. It was found that both the metal extractions were unaffected by the changes in pH. Nickel extraction equilibrium was reached at a longer contact time than that for copper and nickel extraction depends greatly on the extractant concentration in the organic phase. Co-extraction, ammonia scrubbing and selective stripping of copper and nickel were performed for a solution containing 3 g dm^− 3 each of copper and nickel and 60 g dm^− 3 ammonium carbonate. The extraction and the percentage of stripping for nickel and copper were almost quantitative.     

采用N235从镍钼矿盐酸浸出液中萃取钼的研究

采用N235对镍钼矿盐酸浸出液进行了萃取钼的研究。试验结果表明,在最佳工艺条件下,5级逆流钼萃取率可达98%以上,镍损失率小于1%,负载有机相经稀酸洗涤除铁后采用氨水反萃,1级反萃率达97%以上,反萃液钼浓度为50 g/L左右,达到了钼镍分离及钼富集转型的目的。     

Leaching of manganese nodules in ammoniacal medium using glucose as reductant

Polymetallic Indian Ocean nodules can be leached in ammoniacal solution in the presence of glucose. The various parameters chosen for leaching studies were: amount of glucose, time, pH, temperature, concentrations of ammonia and ammonium salt, and particle size. The percentage extraction of copper, nickel and cobalt decreases when the glucose concentration is increased to more than 0.4 gramme per gramme of nodule at 338 K and 0.2 g/g at 358 K. The dissolution of copper has been found to be dependent more on the pH of the solution than on the total molarity of ammonia and the ammonium ion. Leaching temperatures above 373 K are disadvantageous for the extraction of copper and cobalt, whereas nickel extraction is about 95% even at 433 K. The rate of leaching for all three metals is independent of the particle size in the range studied. All the copper, about 90% of the nickel and 60% of the cobalt can be extracted under the following leaching conditions: temperature 358 K, time 4 h, initial ammonia concentration 2.5 M, ammonium chloride concentration 0.37 M and glucose 0.2 gramme per gramme of nodule.     

Enhancement of Nitrate Reduction in Fe0-Packed Columns by Selected Cations

Tests were conducted in Fe0-packed columns to investigate the effects of adding selected cations on nitrate removal by Fe0. Due to a rapid passivation of Fe0, only negligible nitrate was reduced in the columns without adding the selected cation. However, adding certain selected cations (Fe2+, Fe3+, or Al3+) in feed solution can significantly enhance nitrate reduction. Extending hydraulic retention time (HRT) increased nitrate removal by the columns, but the increase was not linearly proportional to HRT. Decreases in columns’ hydraulic conductivity (K) were monitored in an 8?month operating period. A modest decrease in K was recorded in the upper and the middle section of the media bed, whereas a significant decrease in K occurred in the inlet section. X-ray diffraction analyses indicate that magnetite (Fe3O4) was the dominant species of the iron corrosion products in the entire height of the column media under anoxic and other test conditions. In the inlet section, however, lepidocrocite and goethite were also identified. Cementation was found to occur only in the inlet section, suggesting that lepidocrocite and goethite, rather than magnetite, might be responsible for the cementation and thereby cause the hydraulic clogging. The magnetite coating would not necessarily cause clogging of the media.     

竖炉法冶炼含Cr和Ni的铁水试验研究

基于竖炉工艺,以不锈钢除尘灰、铁鳞、红土镍矿、铁精矿和铬矿为主要原料,采用小型试验竖炉进行高温冶炼模拟试验,探索竖炉工艺冶炼含Cr和Ni的铁水的可行性。研究结果表明：采用竖炉法处理不锈钢除尘灰,能实现除尘灰中Fe,Cr和Ni等有价元素的回收。Ni元素基本上全部进入铁水,其回收率高达99.80%,Cr的回收率也可达到95.82%。竖炉全红土矿冶炼含Cr和Ni的铁水是可行的,而且将红土镍矿球团和不锈钢除尘灰球团搭配入炉,不仅可充分回收Fe,Cr和Ni等元素,还可减少渣量、降低焦比。竖炉采用铬矿配加铁精矿球团和铁鳞球团冶炼含Cr铁水时,铁水中Cr质量分数可达到17.5%,最高可达20.48%,Cr回收率稍低,为87.15%,但有进一步提高的可能;随着铁水中Si含量的增加,Cr的回收率逐渐提高,磷的分配比逐渐减低;当铁水Si质量分数从1.38%提高到3.73%时,Cr的回收率和磷的分配比变化不大。