红土镍矿资源现状及其冶炼工艺的研究进展

随着硫化镍矿资源的逐渐减少,高效低成本地开发红土镍矿资源以满足逐渐增加的镍需求有着重要意义。介绍了世界红土镍矿资源现状和特点,并阐述了目前红土镍矿处理的火法工艺、湿法工艺以及其它工艺技术的研究现状及进展,同时分析了这些处理方法的优势与不足,指出了未来的发展方向,以期为低品位红土镍矿的开发提供参考。     

Calcination of low-grade laterite for concentration of Ni by magnetic separation

With the continuous depletion of high-grade nickel ores such as millerite and niccolite, nickeliferous laterites have become the major source for the production of nickel metal. However, only 42% of the world’s production of nickel comes from laterites, since the concentration of Ni is relatively low (ca. 2 wt.%). In addition, other metals, such as magnesium, iron and silicon can be found in laterite, which make the concentration of nickel even more difficult.In this study, a low-grade nickeliferous laterite ore was first calcinated and then processed by using a wet magnetic separator in order to recover nickel. Since, the ore contains both Ni and Fe, the calcination of laterite is effective in altering the crystalline structure of Fe species and therefore its magnetic properties, which in turn enable the selective concentration of nickel by magnetic separation that is an easy and environmentally-friendly technique. The experimental results have indicated the importance of carefully controlling: (1) the calcination temperature; (2) the pulp density and (3) applied magnetic field strength. The main finding of this work was that magnetic separation is effective in recovering 48% of nickel from laterite, increasing the Ni grade in the recovered product from 1.5% to 2.9%, when prior to the separation the ore was calcinated at 500 °C for 1 h.     

Assessing the energy and greenhouse gas footprints of nickel laterite processing

The energy and greenhouse gas footprints of some of the various technologies that are used for processing nickel laterite ores have been assessed using life cycle assessment methodology based largely on publicly reported inventory data. The results of the study were used to identify opportunities to improve the energy and greenhouse gas impacts of the various processes and to examine how they might be affected under different future scenarios such as falling laterite ore grades and the possible imposition of a carbon tax. The opportunities identified included the use of biochar as a fuel and reductant, along with slag waste heat recovery in ferronickel smelting, and the use of the emerging bath smelting technology for ferronickel production instead of the rotary kiln/electric furnace process. As a significant amount of the life cycle-based greenhouse gas emissions from the hydrometallurgical acid leaching processes are generated by acid neutralisation with lime or limestone, there may be opportunities to reduce these emissions by utilising other neutralising agents or possibly by considering non-acid leaching systems. Improving the energy efficiency of the electrowinning stage used to recovery nickel metal from the leach liquor is another possible way in which the sustainability of hydrometallurgical production of nickel from laterite ores could be improved.     

镍矿的处理工艺现状及进展

镍矿是国民经济中一种重要的金属矿产资源,随着经济的发展,人们对镍矿资源的消耗呈逐年上升趋势。目前所查明的镍矿资源中,有近70%的镍矿资源都是硫化镍矿,近30%的镍矿资源属于红土镍矿。随着镍矿资源查明储量的下降,其镍矿资源的综合利用受到越来越多国家的重视。在查阅大量文献的基础上,简要的论述了镍矿资源的总体情况,概述了硫化镍矿常规的处理方法,以及近年来浮选法的一些实际应用及发展。最后,介绍了当前状况下红土镍矿的火法和湿法处理工艺现状及进展,以及一些其他处理镍矿石的方法。为以后镍矿石资源的综合利用和处理工艺的研究提供了一定的参考价值。     

Thermodynamic analysis of the Fe–Ni–Co–Mg–Si–O–H–S–C–Cl system for selective sulphidation of a nickeliferous limonitic laterite ore

An increasing percentage of nickel is being extracted from the laterite ores for which there exists considerable potential for new process development. In the current research, a thermodynamic analysis of the Fe–Ni–Co–Mg–Si–O–H–S–C–Cl system has been performed in order to establish the possible sulphidation conditions for the upgrading of a limonitic laterite ore. The study was performed using the equilibrium module of HSC Chemistry® 6.1, and the data available in the literature were utilised to determine the activity coefficients of the various species employed in the calculations. The effects of variables such as temperature, amount of sulphur and carbon and chlorine additions on both the nickel grade and recovery in the monosulphide solid solution (mss) were determined. Alternative sulphidizing agents were also considered. Nickel recoveries of about 85% could be achieved at a grade of 10% nickel in the mss. Limiting factors in the sulphidation process were the formation of iron sulphide (FeS) and the relatively high stability of nickel oxide in the nickel ferrite (NiFe₂O₄), in comparison to the other phases, which resulted in excessive sulphur requirements of over 100 kg of S/tonne of ore. Methods to overcome these restrictions were discussed and the thermodynamic results were compared to the published experimental values.     

红土镍矿电炉还原炼镍铁合金的研究进展

综述了我国红土镍矿电炉还原炼镍铁的研究进展,重点总结了炼镍铁的机理与研究现状,分析了该技术的难点及其发展趋势。结果表明:红土镍矿中各氧化物的还原先后顺序为NiO>NiFe2O4>Fe2O3>SiO2>MgO。SiO2/MgO在1.6～2.8,FeO含量在20%～30%时,渣与金属密度差异大,且具有良好的流动性,有利于渣与金属分离,提高镍的直收率。渣型对脱硫影响也较大,在碱性渣范围内适当提高炉渣碱度,有利于炉渣脱硫,但是碱度过大会导致渣黏度变大而对脱硫不利。采用电炉还原熔炼工艺生产镍铁具有流程短、镍铁品位易控、金属回收率高的优点,但对于强化冶炼过程、提高作业效率、进一步提高镍铁合金的金属镍含量等问题还有待在生产实践中继续摸索解决。     

红土镍矿冶金技术研究进展

如今世界经济迅猛发展,金属镍的需求量也在加速增长。人们主要从硫化镍矿和红土镍矿中提炼金属镍。然而硫化镍矿资源因大规模开发而不断减少,红土镍矿未来将成为镍的主要来源。因此研究红土镍矿的高效开发利用,是当今围绕镍资源研究的热点,对实际生产具有重要的现实意义。本文简要介绍了镍的应用、开发红土镍矿的意义、红土镍矿的矿物学特性、红土镍矿世界范围内的储量和分布,并且列举并分析了红土镍矿的各种冶炼工艺及其优点与不足,同时综述了有关红土镍矿研究的新方法,为红土镍矿高附加值综合利用研究提出思路。     

Microwave carbothermic reduction roasting of a low grade nickeliferous silicate laterite ore

The known resources of nickel sulphide ores are quickly diminishing and in order to satisfy future nickel demands, nickel laterite deposits are being investigated as an alternative. Currently, expensive leaching and smelting processes are used to process the nickel laterite ores. The objective of the present research was to produce a high grade nickel concentrate via microwave carbothermic reduction roasting followed by magnetic separation. A thermodynamic model was developed for the roasting process in order to determine the optimum experimental conditions. The experimental variables investigated were: microwave energy and argon shrouding for the reduction tests and the magnetic field strength for the concentration stage. The behaviours of nickel and cobalt were studied in the reduction and magnetic separation processes. By optimizing the reducing and magnetic separation conditions, a high grade concentrate containing 9.2% nickel with a nickel recovery of 88.8% was achieved.     

还原-磨选从高镁低品位红土镍矿中回收镍铁

采用还原-磨选工艺对高镁低品位红土镍矿制备镍铁合金粉进行了研究。考察了还原温度、还原时间、原料粒度区间、还原剂用量、添加剂用量等因素对镍直收率的影响。研究结果表明, 合适的还原制度为: 原料粒度0.09～0.12 mm、还原剂用量3%、添加剂用量2.5%, 还原温度1 300 ℃, 还原时间3.0 h。还原产物经球磨、磁选后, 获得镍品位为7.0%以上的镍铁合金粉, 镍直收率87%以上, 实现了从高镁低品位红土镍矿中回收镍铁的目的。     

红土镍矿处理工艺研究现状

随着世界上硫化镍矿资源日趋枯竭以及未来镍需求量不断增长,红土镍矿将成为未来镍的主要来源,因此红土镍矿的有效处理以及高效利用对我国的经济建设有着极大的意义。红土镍矿由于其具有储量丰富、易开采、便于运输等特点,已成为研究开发的热点。本文主要从不同矿层的红土镍矿角度,介绍了当前不同红土镍矿冶炼方法和技术,概述了不同矿层的红土镍矿及其适用的冶炼工艺,分析了不同红土镍矿处理工艺的优势与不足,实现不同类型红土镍矿的综合利用。      

低品质红土镍矿选择性还原-磁选制备镍铁合金

以TFe品位21.70%、Ni品位1.92%的低品位红土镍矿为原料,采用回转窑选择性还原-磁选工艺制备镍铁合金,研究了还原温度、磨矿方式以及磁场强度对镍铁回收率的影响。结果表明,适宜的工艺参数为: 还原温度1150 ℃、细磨(磨矿时间3 min)、磁场强度150 mT,此条件下所得镍铁合金中镍品位7.26%、镍回收率96.06%、铁品位85.15%、铁回收率89.23%,实现了低品位红土镍矿中铁、镍高效回收利用,并且镍铁中碳、磷和硫含量均在要求范围内。     

红土镍矿资源现状及工艺综述

综合论述了世界红土镍矿的资源概况和利用现状,分析了我国对镍的需求情况,对红土镍矿的处理方法和目前有前景的加工工艺进行了较为详细的阐述和分析。     

Reductive dissolution of ferric iron minerals: A new approach for bio-processing nickel laterites

Nickel laterites represent the major ore reserves of this base metal present in the lithosphere. However, processing these ores by conventional technologies involves considerable energy or reagent expenditure and consequently is less cost-effective than extracting nickel from sulfide ores. Biological options, using metal-complexing organic acids and mineral acids generated by fungi and bacteria, have been investigated but generally found to be ineffective in terms of extraction dynamics or yields. We have examined the possibility of using bacteria that can bring about the reductive dissolution of ferric iron minerals and thereby facilitate the extraction of nickel from a lateritic ore at relatively low (<30-45 °C) temperatures.Four species of iron-reducing acidophilic bacteria were screened for their abilities to solubilise nickel from a limonitic laterite ore in which the major iron mineral present was goethite. One of these (Acidithiobacillus ferrooxidans) was selected for further study only the basis of it being able to use a cost-effective energy source (elemental sulfur) to mediate the dissolution of goethite at mildly acidic conditions (pH < 2). Cultures were set up in 2 L bioreactors, maintained at pH 1.8 (±0.1) and 30 °C, and initially aerated (to promote growth of the bacteria on sulfur) and then switched to anaerobic conditions when nickel laterite ore (crushed to <6 mm, with a nickel grade of 0.5%) was added. Over 70% of the nickel present in the ore was solubilised within 14 days, and solubilised metals remained in solution due to the low pH of the leachate. In contrast, only 10% of the nickel was solubilised (by non-reductive acid dissolution) when the cultures were continuously aerated. The results suggest that biological processing of limonitic nickel laterites is technically feasible and, more generically, that reductive dissolution can be used to bioprocess ferric oxide mineral ores.     

某高镁低铁镍型红土镍矿石转底炉法还原提镍试验

某高镁低铁镍型红土镍矿石Fe、Ni品位分别为17.68%和1.62%，MgO含量为19.06%，镍主要以类质同象形式取代Fe、Mg存在于铁氧化物和硅酸盐矿物中，占比分别为39.65%和54.72%。为了确定该矿石的高效开发利用工艺，通过小型基础试验确定还原焙烧和磨选工艺参数，再在中径8 m的转底炉上进行还原焙烧中试试验。结果表明：试样采用煤基直接还原-水淬冷却-2阶段磨矿弱磁选工艺处理，在红土镍矿、石灰石、TN的质量配比为100∶10∶3，按碳氧物质的量之比1.2配入无烟煤，还原焙烧温度为1 280 ℃，还原焙烧时间为40 min，还原焙烧熟料水淬产品一段磨矿细度为-0.074 mm占83.31%，一段弱磁选磁场强度为190.98 kA/m，二段磨矿细度为-0.074 mm占97.43%，二段弱磁选磁场强度为127.32 kA/m的情况下，获得了Ni品位为5.63%、Fe品位为60.39%、Ni回收率为80.83%、Fe回收率为75.14%的镍铁粉；中径8 m的转底炉中试产品经磨选，获得了Ni品位为5.26%、Fe品位为59.20%、Ni回收率为80.84%、Fe回收率为74.98%的镍铁粉。该研究成果可作为工程化的依据，也为同类型红土镍矿石资源的高效开发利用提供了技术借鉴。     

Selective sulphidation of a nickeliferous lateritic ore

The processing of nickeliferous laterites to produce nickel metal is both complex and energy intensive. Since most laterites are found in less developed regions, the capital costs for the infrastructure can exceed those for the process itself. The low temperature sulphidation of lateritic ores to produce an intermediate nickel concentrate, for further processing, offers a number of potential advantages, such as lower energy consumption and a relatively simple flowsheet. In this research, the sulphidation of a nickeliferous lateritic ore was investigated between the temperatures of 450-1000 °C and sulphur additions of between 25 and 900 kg of sulphur per tonne of ore. The experiments showed that the nickel oxide can be selectively sulphidized to a nickel-iron sulphide. It was found that both the grade and the sulphidation degree largely depended upon the temperature and the sulphur additions, with temperatures above 550 °C exhibiting the highest recoveries and grades. A DTA/TGA with mass spectrometer was used to further elucidate the nature of the phase transformations that occur upon heating of the ore in the presence of sulphur.     

Microwave heating behaviour of nickeliferous limonitic laterite ores

The nickeliferous laterite ores, in which the nickel occurs in oxide form, represent a significant potential resource of metallic nickel. However, in comparison to the nickel-containing sulfide ores, the extraction costs are relatively high and thus it will be necessary to develop new processing techniques, which are both technically and economically viable. In the present research, the potential application of microwaves for the heating of a nickeliferous limonitic laterite ore ((Fe,Ni)O(OH) · nH₂O) was investigated. Firstly, since the nickeliferous limonitic laterite ore contains considerable moisture, both free and combined, then thermogravimetric analysis (TGA) was performed in order to characterize the changes, which result from the dehydration processes. Derivative thermogravimetric analysis (DTGA) curves were calculated from the TGA data. Secondly, the real (ε^′) and imaginary (ε^″) permittivities of the ore were measured at frequencies of 912 and 2460 MHz at temperatures up to about 1000 °C using the cavity perturbation technique and these results were related to the DTGA curves. Also, the loss tangent (tanδ=ε^″/ε^′) was calculated from the permittivity data. Finally, the microwave heating behaviour of the nickeliferous limonitic laterite ore was determined at 2460 MHz.The results show that the both the real (ε^′) and imaginary permittivities (ε^″) and the loss tangent (tanδ) increase with temperature and change as both the free and the combined moisture are removed. The permittivities (ε^′ and ε^″) increased with increasing slope of the TGA curve and vice versa during the goethite to hematite dehydroxylation reaction, where there was a maximum in the permittivities (ε^′ and ε^″). It is proposed that these changes, which occur during the dehydroxylation reaction, are a result of the liberation of hydroxyl units from the goethite structure. Furthermore, some hydroxyl units were retained in the hematite structure (i.e. hydrohematite (α-Fe_2−x/3O_3−xOH_x)) even after the goethite to hematite transition and thus the permittivities of the dehydroxylated ore were higher than that of normal hematite. With regards, to their microwave heating behaviour, it is shown that despite the relatively low permittivities (ε^′ and ε^″) of these materials at low temperatures, they can be heated using microwaves. The microwave heating process can be improved by conventional preheating of the sample or by the addition of charcoal as a susceptor or by selecting a crucible material, which acts as a susceptor. There is a rapid increase in the permittivities over the temperature range of about 600–800 °C and this combined with the low thermal conductivities of these oxides, can result in rapid internal heating of the sample and thermal runaway.     

红土镍矿加压酸浸工艺进展

随着硫化镍矿资源的逐渐减少,高效且低成本的开发红土镍矿资源以满足逐渐增加的镍需求有着重要意义。据此,本文首先介绍了红土镍矿的矿物学特性及其加压酸浸工艺的反应机理,并从提高镍浸出率、降低酸耗角度概述了该工艺的影响因素;其次从工业应用角度介绍了该工艺的技术改进,着重介绍了加压酸浸—常压酸浸工艺(HPAL-AL)和非常规介质浸出工艺。     

The effect of sodium sulphate on the hydrogen reduction process of nickel laterite ore

A series of nickel laterite ores with different calculated amounts of anhydrous sodium sulphate were prepared by physical blending or sodium sulphate solution impregnation. The reduction of the prepared nickel laterite ore by H₂ was carried out in a fluidised-bed reactor with provisions for temperature and agitation control, and the magnetic separation of the reduced ore was performed using a Davis tube magnetic separator. The mineralogical properties of the raw laterite ore, reduced ore and magnetic concentrate were characterised using ICP, TG–DSC, N₂ adsorption, X-ray diffraction and optical microscopy. The catalytic activity of sodium sulphate was also studied by using Hydrogen temperature-programed reduction. The experimental results indicate that Na₂SO₄ could overcome the kinetic problems faced by the laterite ore and that it exhibited noticeable catalytic activity only if the temperature reached at least 750 °C. This high temperature accelerated the crystal phase transition of the silicate minerals and increased the utilisation of H₂. In comparing the results from the two different methods for adding Na₂SO₄, the nickel content and recovery of the magnetic concentrate were increased by using the impregnation method rather than the physical blending method and the increasing amount of sodium sulphate assisted in the further beneficiation of nickel. The partial pressure of H₂ and the reducing time also affected the reduction process of the iron oxides. The results of the microscopic study indicated that the formation of a Fe–S solid solution, which was derived from the SO₂ sulphide reduction of FeO, was conducive to mass transfer and accelerated the coalescence of metallic ferronickel particles. For the nickel laterite ore, under the synergistic effect of sodium sulphate and hydrogen, a nickel content and nickel recovery of 6.38% and 91.07% were obtained, respectively, with high product selectivity.     

氯化钙作用下镁质贫镍红土矿选择性富集镍的研究

采用还原焙烧-磁选工艺, 对氯化钙作用下镁质贫镍红土矿选择性富集镍进行了研究, 考察了还原温度、还原时间、还原剂用量和氯化钙用量对富集镍的影响。结果表明, 在还原温度1 200 ℃、还原时间40 min、还原剂和氯化钙用量均为8%的条件下, 可获得镍品位8.67%、回收率92.01%的镍铁精矿; 相比于直接还原焙烧-磁选, 加入8%氯化钙后使镍的富集比由3增加到11, 显著提高了镍的富集效果。磁选产品物相分析显示, 镍主要以铁纹石形式存在于精矿中, 通过磁选实现了对镍铁精矿与脉石的有效分离。     

印尼某低品位红土镍矿的热解性能

为提高红土镍矿火法冶炼工艺技术指标,对印尼某低品位红土镍矿进行了热解性能分析。结果表明：该红土镍矿属于典型的低品位过渡层红土镍矿,主要组成矿物为利蛇纹石、针铁矿、石英、铁蛇纹石、叶蛇纹石和高岭石,镍主要赋存于蛇纹石、橄榄石等硅酸盐类矿物中,部分以氧化镍形式赋存于针铁矿中。红土镍矿热解分析结果表明：在86 ℃时有1次失重过程,形成1个吸热峰,有H2O溢出,对应自由水的脱除;在268 ℃时有1次失重过程,形成1个吸热峰,有H₂O溢出,对应针铁矿的脱羟基过程;在589 ℃时发生失重,形成1个吸热峰,有H₂O溢出,对应高岭石、利蛇纹石的脱羟基反应;在816 ℃时有1个放热峰,而红土镍矿质量没有变化,对应利蛇纹石热解产生无定型的硅酸盐重结晶后产生镁橄榄石（Mg₂SiO₄）及顽火辉石（MgSiO₃）的过程;在1 126 ℃时有1次失重过程,有CO₂溢出,由白云石分解产生。试验结果对红土镍矿火法工艺的改进有指导作用。