Feasibility of co-reduction roasting of a saprolitic laterite ore and waste red mud

Large scale utilization is still an urgent problem for waste red mud with a high content of alkaline metal component in the future. Laterite ores especially the saprolitic laterite ore are one refractory nickel resource, the nickel and iron of which can be effectively recovered by direct reduction and magnetic separation. Alkaline metal salts were usually added to enhance reduction of laterite ores. The feasibility of co-reduction roasting of a saprolitic laterite ore and red mud was investigated. Results show that the red mud addition promoted the reduction of the saprolitic laterite ore and the iron ores in the red mud were co-reduced and recovered. By adding 35wt% red mud, the nickel grade and recovery were 4.90wt% and 95.25wt%, and the corresponding iron grade and total recovery were 71.00wt% and 93.77wt%, respectively. The X-ray diffraction (XRD), scanning electron microscopy, and energy dispersive spectroscopy (SEM-EDS) analysis results revealed that red mud addition was helpful to increase the liquid phase and ferronickel grain growth. The chemical compositions “CaO and Na₂O” in the red mud replaced FeO to react with SiO₂ and MgSiO₃ to form augite.     

Recovery of iron from high phosphorus oolitic iron ore using coal-based reduction followed by magnetic separation

Oolitic iron ore is one of the most important iron resources. This paper reports the recovery of iron from high phosphorus oolitic iron ore using coal-based reduction and magnetic separation. The influences of reduction temperature, reduction time, C/O mole ratio, and CaO content on the metallization degree and iron recovery were investigated in detail. Experimental results show that reduced products with the metallization degree of 95.82% could be produced under the optimal conditions (i.e., reduction temperature, 1250℃; reduction time, 50 min; C/O mole ratio, 2.0; and CaO content, 10wt%). The magnetic concentrate containing 89.63wt% Fe with the iron recovery of 96.21% was obtained. According to the mineralogical and morphologic analysis, the iron minerals had been reduced and iron was mainly enriched into the metallic iron phase embedded in the slag matrix in the form of spherical particles. Apatite was also reduced to phosphorus, which partially migrated into the metallic iron phase.     

红土镍矿深度还原-磁选富集镍铁实验研究

采用深度还原-磁选工艺,以煤粉为还原剂,添加氧化钙作助溶剂,在微熔化,不完全造渣的条件下,将矿石中镍和铁的氧化物还原成金属镍铁,然后经磁选方法使金属镍铁在磁性产品中得到富集.结果表明,深度还原最佳工艺条件为:还原温度1 300℃,还原时间60 min,配煤过剩倍数2.在此工艺条件下得到镍、铁质量分数分别为5.01%,22.46%的镍铁产品,镍、铁回收率分别为96.05%,79.69%.对深度还原过程研究表明,还原物料中镍和铁以金属合金颗粒形式存在,高温有利于镍铁金属相凝聚,适当延长还原反应时间有利于镍铁颗粒的还原和聚集长大,进而有利于磁选富集.     

Dolochar as a reductant in the reduction roasting of iron ore slimes

The present investigation examines the viability of dolochar, a sponge iron industry waste material, as a reductant in the reduction roasting of iron ore slimes, which are another waste generated by iron ore beneficiation plants. Under statistically determined optimum conditions, which include a temperature of 900℃, a reductant-to-feed mass ratio of 0.35, and a reduction time of 30-45 min, the roasted mass, after being subjected to low-intensity magnetic separation, yielded an iron ore concentrate of approximately 64wt% Fe at a mass recovery of approximately 71% from the feed iron ore slime assaying 56.2wt% Fe. X-ray diffraction analyses indicated that the magnetic products contain magnetite and hematite as the major phases, whereas the nonmagnetic fractions contain quartz and hematite.     

石油焦作还原剂对低品位红土镍矿与赤泥共还原制备镍铁的影响

石油焦作为工业固体废物,其堆积和储存对生态环境产生巨大的影响。本文对石油焦在低品位红土镍矿与赤泥共还原过程中用作还原剂的可行性及其机理进行了研究。通过研究石油焦用量、焙烧温度和焙烧时间等对红土镍矿与赤泥共还原过程的影响,确定最佳的工艺条件为石油焦用量20wt%、焙烧温度1250°C、焙烧时间60 min。在此条件下,可以获得镍品位1.96wt%、铁品位85.76wt%、镍回收率97.83wt%、铁回收率96.81wt%的镍铁产品。扫描电镜和能谱(SEM–EDS)分析结果表明,红土镍矿与赤泥共还原过程中镍和铁主要以镍铁颗粒的形式存在,镍铁颗粒分布均匀且纯度很高,粒径约30 μm。结果表明,石油焦作为还原剂用于红土镍矿和赤泥共还原是可行的,与无烟煤作还原剂相比,石油焦具有成本低的优点。研究结果不仅为石油焦的利用提供了一个新途径,同时也为缺煤地区红土镍矿与赤泥共还原工艺的利用提供了一种解决方案。     

Metalizing reduction and magnetic separation of vanadium titano-magnetite based on hot briquetting

To achieve high efficiency utilization of Panzhihua vanadium titano-magnetite, a new process of metalizing reduction and magnetic separation based on hot briquetting is proposed, and factors that affect the cold strength of the hot-briquetting products and the efficiency of reduction and magnetic separation are successively investigated through laboratory experiments. The relevant mechanisms are elucidated on the basis of microstructural observations. Experimental results show that the optimal process parameters for hot briquetting include a hot briquetting temperature of 475℃, a carbon ratio of 1.2, ore and coal particle sizes of less than 74 μm. Additionally, with respect to metalizing reduction and magnetic separation, the rational parameters include a magnetic field intensity of 50 mT, a reduction temperature of 1350℃, a reduction time of 60 min, and a carbon ratio of 1.2. Under these above conditions, the crushing strength of the hot-briquetting agglomerates is 1480 N, and the recovery ratios of iron, vanadium, and titanium are as high as 91.19%, 61.82%, and 85.31%, respectively. The new process of metalizing reduction and magnetic separation based on hot briquetting demonstrates the evident technological advantages of high efficiency separation of iron from other valuable elements in the vanadium titano-magnetite.     

高浓度NaOH浸出红土镍矿中SiO_2的研究

研究了红土镍矿高浓度NaOH浸出的条件.探讨了搅拌强度、温度、NaOH初始质量分数、浸出时间和碱矿质量比对SiO2浸出率的影响.结果表明:搅拌强度600 r/min、浸出温度225℃、初始NaOH质量分数85%、浸出时间90 min、碱矿比5∶1时,SiO2的浸出率可达82.77%.碱浸渣中的铁、镁、镍被富集,其中氧化镍的质量分数由1.29%提高到2.15%.     

CaF2强化红土镍矿自还原过程中金属相聚集长大行为

针对高镁高硅型中低品位红土镍矿,采用煤基自还原-细磨-磁选工艺制备镍铁粉,研究了内配碳比对红土镍矿中铁、镍氧化物自还原的影响,CaF_2对红土镍矿自还原过程中氧化物的还原、金属相的析出及聚集长大的影响规律。研究表明在CaF_2作用下通过降低内配碳比可抑制氧化铁的还原,从而获得镍品位较高的镍铁粉,但相应牺牲镍的回收率;CaF_2能与红土镍矿中高熔点的硅酸盐脉石通过固相反应生成低熔点的透闪石(Ca_2Mg_5(Si_4O_(11))_2F_2),使硅酸盐矿物结构由岛状转变为链状,提高硅酸盐矿物反应活性,促进镍、铁氧化物的还原;通过降低红土镍矿脉石相的熔化性温度,CaF_2能明显强化红土镍矿自还原过程中金属相的析出、聚集和长大,促进镍铁与脉石的有效分离,从而大幅度提高镍铁粉中镍和铁的品位及金属元素的回收率。     

Extraction and separation of nickel and cobalt from saprolite laterite ore by microwave-assisted hydrothermal leaching and chemical deposition

Extraction and separation of nickel and cobalt from saprolite laterite ore were studied by using a method of microwave-assisted hydrothermal leaching and chemical deposition. The effects of leaching temperature and time on the extraction efficiencies of Ni2+ and Co2+ were investigated in detail under microwave conditions. It is shown that the extraction efficiencies of Ni2+ and Co2+ from the ore pre-roasted at 300℃ for 5 h were 89.19% and 61.89% when the leaching temperature and time were about 70℃ and 60 min, respectively. For the separation process of Ni and Co, the separation of main chemical components was performed by adjusting the pH values of sulfuric leaching solutions using a NaOH solution based on the different pH values of precipitation for metal hydroxides. The final separation efficiencies of Ni and Co were 77.29% and 65.87%, respectively. Furthermore, the separation efficiencies of Fe of 95.36% and Mg of 92.2% were also achieved at the same time.     

Effects of Na<Subscript>2</Subscript>SO<Subscript>4</Subscript> on iron and nickel reduction in a high-iron and low-nickel laterite ore

This study investigates the reactions of Na₂SO₄ and its effects on iron and nickel reduction in the roasting of a high-iron and low-nickel laterite ore through gas composition, X-ray diffraction, and scanning electron microscope analyses. Results showed that a reduction reaction of Na₂SO₄ to SO₂ was performed with roasting up to 600℃. However, no clear influence on iron and nickel reductions appeared, because only a small amount of Na₂SO₄ reacted to produce SO₂. Na₂SO₄ reacted completely at 1000℃, mainly producing troilite and nepheline, which remarkably improves selective reduction of nickel. Furthermore, the production of low-melting-point minerals, including troilite and nepheline, accelerated nickel reduction and delayed iron reduction, which is attributed to the concurrent production of magnesium magnetite, whose structure is more stable than the structure of magnetite. Reduction reactions of Na₂SO₄ resulted in weakening of the reduction atmosphere, and the main product of Na₂SO₄ changed and delayed the reduction of iron. Eventually, iron metallization was effectively controlled during laterite ore reduction roasting, leading to iron mainly being found in wustite and high iron-containing olivine.     

Preparation of ferronickel from nickel laterite via coal-based reduction followed by magnetic separation

The sticking phenomenon between molten slag and refractory is one of the crucial problems when preparing ferronickel from laterite ore using rotary hearth furnace or rotary kiln processes. This study aims to ameliorate sticking problems by using silicon dioxide (SiO₂) to adjust the melting degree of the briquette during reduction roasting. Thermodynamic analysis indicates that the melting temperature of the slag gradually increases with an increase in the SiO₂ proportion (SiO₂/(SiO₂ + Al₂O₃ + MgO) mass ratio). Experimental validations also prove that the briquette retains its original shape when the SiO₂ proportion is greater than 75wt%, and sticking problems are avoided during reduction. A ferronickel product with 8.33wt% Ni and 84.71wt% Fe was prepared via reductive roasting at 1500℃ for 90 min with a SiO₂ proportion of 75wt% and a C/O molar ratio of 1.0 followed by dry magnetic separation; the corresponding recoveries of Ni and Fe reached 75.70% and 77.97%, respectively. The microstructure and phase transformation of reduced briquette reveals that the aggregation and growth of ferronickel particles were not significantly affected after adding SiO₂ to the reduction process.     

Comprehensive recovery of lead,zinc, and iron from hazardous jarosite residues using direct reduction followed by magnetic separation

Lead, zinc, and iron were recovered from jarosite residues using direct reduction followed by magnetic separation. The influence of the coal dosage, reduction temperature, and reduction time on the volatilization rates of lead and zinc and the metallization rate of iron were investigated. The results show that the volatilization rates of lead and zinc were 96.97% and 99.89%, respectively, and the iron metallization rate was 91.97% under the optimal reduction roasting conditions of a coal dosage of 25.0wt% and reduction roasting at 1250℃ for 60 min. The magnetic concentrate with an iron content of 90.59wt% and an iron recovery rate of 50.87% was obtained under the optimum conditions in which 96.56% of the reduction product particles were smaller than 37 μm and the magnetic field strength was 24 kA/m. Therefore, the results of this study demonstrate that recovering valuable metals such as lead, zinc, and iron from jarosite residues is feasible using the developed approach.     

红土镍矿还原熔炼制备镍铁的试验研究

对低铁、高硅、高镁腐殖土型红土镍矿的脱水和碳还原过程进行DTA-TG分析,确定脱水和固体碳还原反应的温度区间。在煅烧-还原熔炼红土镍矿制备镍铁中,针对矿石自然渣型碱度低、黏度及密度大,不利于金属与渣分离及镍回收率提高等问题,采用控制CaO加入量的方法,调节CaO-FeO-MgO-SiO2系炉渣的黏度和密度;探讨还原剂焦粉及CaO用量、温度、时间对熔炼效果的影响。综合考虑镍铁品位和镍的回收率,确定最佳还原熔炼试验条件:焦粉、石灰与矿石质量比分别为9.0%和8.3%,温度为1 550℃,时间为40 min。在最佳试验条件下,产出的镍铁品位为22.0%,镍、钴回收率分别为92.5%和70.0%。     

Carbothermic reduction characteristics of ludwigite and boron-iron magnetic separation

Ludwigite is a kind of complex iron ore containing boron, iron, and magnesium, and it is the most promising boron resource in China. Selective reduction of iron oxide is the key step for the comprehensive utilization of ludwigite. In the present work, the reduction mechanism of ludwigite was investigated. The thermogravimetry and differential scanning calorimetry analysis and isothermal reduction of ludwigite/coal composite pellet were performed. Ludwigite yielded a lower reduction starting temperature and a higher final reduction degree compared with the traditional iron concentrates. Higher specific surface area and more fine cracks might be the main reasons for the better reducibility of ludwigite. Reducing temperature highly affected the reaction fraction and microstructure of the reduced pellets, which are closely related to the separation degree of boron and iron. Increasing reducing temperature benefited the boron and iron magnetic separation. Optimum magnetic separation results could be obtained when the pellet was reduced at 1300℃. The separated boron-rich non-magnetic concentrate presented poor crystalline structure, and its extraction efficiency for boron reached 64.3%. The obtained experimental results can provide reference for the determination of the comprehensive utilization flow sheet of ludwigite.     

硫酸钠对高铁型红土镍矿中铁矿物还原的抑制机理

研究了硫酸钠对红土镍矿中铁矿物还原的抑制机理。结果发现硫酸钠能够改变铁矿物的还原历程，生成FeS和含铁的铝硅酸盐，使焙烧矿液相增加。液相的增加抑制煤的气化反应，减弱体系的还原气氛，同时抑制还原气体的扩散，对铁矿物的还原不利。 FeS和铝硅酸盐形成的液相包裹在FeO周围使其还原受到抑制，铝硅酸盐在包裹FeO的同时与其反应生成更多液相，对FeO的还原起到进一步的抑制作用。     

铬铁矿的还原焙烧与磁选分离

以南非铬铁矿为原料,以潞安煤粉为还原剂,进行了铬铁矿粉还原焙烧与磁选分离实验。借助扫描电镜、能谱分析和X射线衍射分析,对碳热还原和磁选分离过程中的物相变化进行了系统研究。实验发现,当温度低于1 200℃时,铬铁矿仅发生少量铁氧化物的还原,当温度高于1 300℃时,铬铁矿中铬氧化物开始被还原成碳化铬。随着还原反应的不断进行,铬铁尖晶石结构逐渐发生转变并被破坏。在本实验条件下,铬铁矿较为适宜的预处理温度为1 200℃,此温度下的还原产物磁选后,磁选产物几乎全部为金属铁,磁选所得尾渣的除铁率为46%,铬的收得率为80%,w(Cr2O3)/w(ΣFe O)值高达3.75。研究工作对于铬铁矿预处理工艺的设计开发及低品位铬铁矿的综合利用具有理论指导意义。     

红土镍矿焙烧过程中的矿相转变及其对气体还原的影响

研究了印度尼西亚红土镍矿焙烧过程中的矿相转变过程以及焙烧温度对混合气体 (V (CO) : V (O₂)=50 : 50)还原的影响. 采用差热/热重分析(differential scanning calorimeter/thermal gravimetric, DSC/TG)、比表面积分析法(Brunauer Emmett Teller, BET)、X射线衍射(X-ray diffraction, XRD)、扫描电镜(scanning electron microscope, SEM)等方法综合考察了各因素对红土镍矿焙烧过程及其对后续还原的影响. 结果表明: 在焙烧阶段, 红土镍矿中的针铁矿在 300°C 左右脱除结晶水形成赤铁矿, 600~700 °C时蛇纹石分解形成无定形态硅镁酸盐, 且当温度继续升高时无定形态硅镁酸盐会结晶形成橄榄石; 利用混合气体 (V (CO) : V (O2)=50 : 50)还原红土镍矿时, 随着焙烧温度的升高, 镍和铁的金属化率也逐渐升高, 经700°C焙烧后, 还原产物镍的金属化率最高可达86.81%, 但是当焙烧温度超过橄榄石结晶温度时则不利于红土镍矿的还原, 镍的金属化率降至66.73%.     

Kinetics of thermal decomposition of hydrated minerals associated with hematite ore in a fluidized bed reactor

The kinetics of removal of loss on ignition (LOI) by thermal decomposition of hydrated minerals present in natural iron ores (i.e., kaolinite, gibbsite, and goethite) was investigated in a laboratory-scale vertical fluidized bed reactor (FBR) using isothermal methods of kinetic analysis. Experiments in the FBR in batch processes were carried out at different temperatures (300 to 1200℃) and residence time (1 to 30 min) for four different iron ore samples with various LOIs (2.34wt% to 9.83wt%). The operating velocity was maintained in the range from 1.2 to 1.4 times the minimum fluidization velocity (U_mf). We observed that, below a certain critical temperature, the FBR did not effectively reduce the LOI to a desired level even with increased residence time. The results of this study indicate that the LOI level could be reduced by 90% within 1 min of residence time at 1100℃. The kinetics for low-LOI samples (<6wt%) indicates two different reaction mechanisms in two temperature regimes. At lower temperatures (300 to 700℃), the kinetics is characterized by a lower activation energy (diffusion-controlled physical moisture removal), followed by a higher activation energy (chemically controlled removal of LOI). In the case of high-LOI samples, three different kinetics mechanisms prevail at different temperature regimes. At temperature up to 450℃, diffusion kinetics prevails (removal of physical moisture); at temperature from 450 to 650℃, chemical kinetics dominates during removal of matrix moisture. At temperatures greater than 650℃, nucleation and growth begins to influence the rate of removal of LOI.     

蛇纹石型红土矿常压酸浸实验研究

主要探讨了常压下盐酸对蛇纹石型红土镍矿进行浸出的工艺条件。考察了酸矿比、液固比、反应温度、反应时间等对蛇纹石型红土镍矿浸出的影响。通过实验得出最佳工艺条件:酸矿比为2.5∶1、液固比为5∶1、反应时间为0.5 h、反应温度为100℃。在此条件下镍、钴、铁浸出率分别为100%、100%和90%。     

Multi-index analysis of the melting process of laterite metallized pellet

Herein, a multi-index analysis of the nickel content of an alloy, output rate of the alloy, nickel recovery rate, and iron recovery rate during the melting of laterite metallized pellets was performed. The thermodynamic reduction behavior of oxides such as NiO, FeO, Fe₃O₄, and Cr₂O₃ was studied using the FactSage software, which revealed that SiO₂ is not conducive to the reduction of iron oxides, whereas the addition of basic oxides such as CaO and MgO is beneficial for the reduction of iron oxides. On the basis of a comprehensive analysis to achieve greater nickel recovery and lower iron recovery rates, the optimum experimental parameters in the orthogonal experiment were A3B1C3 (t=30 min, C/O=0.4, R=1.2); the indicators w_Ni, φ_alloy, η_Ni, and η_Fe had values of 15.0wt%, 12.1%, 44.9%, and 96.4%, respectively. In single-factor experiments, increasing basicity (R) substantially improved the separation effect in the low-basicity range 0.5 ≤ R ≤ 0.8 but not in the high-basicity range 0.8 ≤ R ≤ 1.2. Similar results were obtained for the effect of the C/O ratio. Moreover, the recovery rate of nickel increased with increasing recovery rate of iron.