Study on mechanisms of different sulfuric acid leaching technologies of chromite

The extraction of chromate from chromite via the sulfuric acid leaching process has strong potential for practical use because it is a simple and environmentally friendly process. This paper aims to study the sulfuric acid leaching process using chromite as a raw material via either microwave irradiation or in the presence of an oxidizing agent. The results show that the main phases in Pakistan chromite are ferrichromspinel, chrompicotite, hortonolite, and silicate embedded around the spinel phases. Compared with the process with an oxidizing agent, the process involving microwaves has a higher leaching efficiency. When the mass fraction of sulfuric acid was 80% and the leaching time was 20 min, the efficiency could exceed 85%. In addition, the mechanisms of these two technologies fundamentally differ. When the leaching was processed in the presence of an oxidizing agent, the silicate was leached first and then expanded. By contrast, in the case of leaching under microwave irradiation, the chromite was dissolved layer by layer and numerous cracks appeared at the particle surface because of thermal shock. In addition, the silicate phase shrunk instead of expanding.     

低m(Cr)/m(Fe)铬铁矿除铁工艺的实验研究

以南非铬铁矿为对象,在热力学分析的基础上,采用碳热还原法开展了低m(Cr)/m(Fe)铬铁矿除铁工艺的实验研究.结果表明:实验中铬铁矿选择性除铁的适宜温度为1 100℃左右,符合热力学计算结果.低于此温度时还原出的富铁相与基体分离不彻底,难以结瘤析出;高于此温度时尖晶石相中的铬元素还原严重,影响铬的回收率.在1 100℃还原0.5 h并经酸浸处理后,铬铁矿可由化工级提升至冶金级,在相同温度下还原2 h后,m(Cr)/m(Fe)可由1.7提高至5.8,为实现低m(Cr)/m(Fe)铬铁矿的高效利用提供了新思路.     

铀矿堆浸过程的动力学模型及实验研究

通过浸出率与浸出时间的关系曲线,推导出铀矿硫酸堆浸过程的控制模式和化学反应常数。实验结果表明浸出率在小于60％以内,与浸出时间呈直线关系,得出浸出过程控制模式为化学反应控制的结论。实验数据计算得出在该实验中化学反应浸出速率常数为1．5×10^-7s^-1,液固相化学反应速率系数为3．6×10^-8m／s。实验结果在未加氧化剂的酸堆浸铀矿石中,最多只有40％的四价铀能氧化成六价铀,要想进一步提高铀的浸出率,必须加入氧化剂,提高氧化能力。     

硝酸“催化”分解黄铁矿的动力学研究

本文在333～363K,硝酸根浓度0.1～0.5mol/L的条件下,实验研究了常氧压下硝酸“催化”分解黄铁矿的动力学。结果表明,黄铁矿分解后其中所含硫主要转化为硫酸根,浸出过程受化学反应控制,符合收缩未反应核模型,其表观活化能为39.87kJ/mol。根据实验结果推导出浸出速率的数学模型为: 1-(1-α)~(1/3)=6.30×10~2C_(NO_3)~(0.83)·C_H~(0.81)·r_0~(-1)·exp(-39.87×10~3/RT)t     

内蒙古索伦山地区地幔橄榄岩中豆荚状铬铁找矿前景

产于内蒙古索伦山缝合带蛇绿岩中的铬铁矿,其深入研究对于铬铁矿的勘查、缓解铬铁矿需求紧张、增加战略矿产资源以及国民经济的发展,意义重大。本文对内蒙古索伦山地区铬铁矿进行了系统的调查和研究,在此基础上,总结了索伦山地区铬铁矿矿床地质特征,探讨了索伦山地区铬铁矿矿床的成因,评价了在索伦山地区铬铁矿找矿远景。索伦山地区铬铁矿均分布于索伦山蛇绿岩之地幔橄榄岩内,矿体产出众多,规模大小不等,均具有成带分布、分段集中的特点。矿体产状与方辉橄榄岩-纯橄榄岩产状基本一致,矿体与围岩为渐变过渡的关系。索伦山地区铬铁矿为产出高镁型矿石类型的豆荚状铬铁矿,形成于早二叠世,产于大洋中脊的构造环境。通过对地幔橄榄岩与铬铁矿的岩石学、矿物学、地球化学研究,表明索伦山地区铬铁矿的成因为熔体-岩石反应。在索伦山地区探明铬铁矿矿化点2个,铬铁矿矿点10个,小型铬铁矿矿床10个。10个已查明的小型铬铁矿矿床表明,地表矿少,盲矿体多。据此推断,已经查明的12个铬铁矿矿(化)点有可能探到更多更大的深部工业盲矿体。索伦山含铬超镁铁岩体规模巨大,延深大于600 m,具备良好的成矿条件,是良好的铬铁矿找矿靶区,具有较好的找矿前景。     

基于不同粒级硫化铜矿石生物浸出的动力学

西藏甲玛地区的硫化铜矿石中含铜矿物以次生硫化铜矿物为主,且含量较低.采用氧化亚铁硫杆菌柱浸的方法对该矿石进行了生物浸出并研究了浸出动力学.基于不同粒级矿石,考察了粒级对铜浸出速率和浸出率的影响,并对浸出率与收缩核模型中的控制方程进行了拟合,确定了浸出过程的控速环节.试验结果表明,铜的浸出速率和浸出率随粒级的减小而增加.矿石表面形貌的SEM表明,浸出过程中矿石表面形成了包含黄钾铁矾的产物层,阻碍了浸出反应的进行.浸出动力学表明,该矿石的浸出过程符合收缩核模型,且浸出应主要受固体产物层内扩散控制.     

Decomposition mechanism of chromite in sulfuric acid-dichromic acid solution

The sulfuric acid leaching process is regarded as a promising, cleaner method to prepare trivalent chromium products from chromite; however, the decomposition mechanism of the ore is poorly understood. In this work, binary spinels of Mg-Al, Mg-Fe, and Mg-Cr in the powdered and lump states were synthesized and used as raw materials to investigate the decomposition mechanism of chromite in sulfuric acid-dichromic acid solution. The leaching yields of metallic elements and the changes in morphology of the spinel were studied. The experimental results showed that the three spinels were stable in sulfuric acid solution and that dichromic acid had little influence on the decomposition behavior of the Mg-Al spinel and Mg-Fe spinel because Mg2+, Al3+, and Fe3+ in spinels cannot be oxidized by Cr6+. However, in the case of the Mg-Cr spinel, dichromic acid substantially promoted the decomposition efficiency and functioned as a catalyst. The decomposition mechanism of chromite in sulfuric acid-dichromic acid solution was illustrated on the basis of the findings of this study.     

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。     

墨西哥某氧化铜矿形态学特征对其酸浸试验的影响

通过化学选矿的方法研究了氧化铜矿形态学特征对铜浸出率的影响.以硫酸为浸出剂对某氧化铜矿的两种矿样进行酸浸试验.分别研究浸出剂用量、浸出时间以及料层厚度等影响因素.同时,采用扫描电子显微镜（SEM）观察原矿和尾矿中铜的形态学特征,即A矿样中铜矿物以薄膜的形式覆盖在脉石矿物表面;B矿样中铜矿物呈颗粒状与脉石矿物共生.酸浸试验结果表明：在相同的条件下,A矿样的铜浸出率要远高于B矿样.这是因为A矿样中铜矿物具有更大的比表面积,与硫酸的接触面大,反应更加充分.     

微生物催化大洋多金属结核和黄铁矿共同浸出及反应动力学模型

为了直观地表征大洋多金属矿微生物浸出过程中各因素的相互关系,进行了微生物催化MnO2-FeS2-H2SO4体系的好氧和厌氧浸出实验,利用DLVO理论建立厌氧条件下微生物催化浸出氧化锰矿物中有价金属的动力学模型--收缩核模型.微生物在厌氧条件下催化大洋多金属矿和黄铁矿的氧化还原反应,浸出锰的机理是细菌催化铁离子在二价和三价的循环转化;微生物吸附在矿物表面加速反应的进程,矿物颗粒在反应中不断缩小.进一步实验表明收缩核模型曲线与实验曲线拟合较好,验证了模型的可靠性.     

瑞木红土矿摇床铬铁矿粗精的磁选富集

瑞木红土矿中存在含铬尖晶石矿物,在进行矿浆管道输送和高压浸出之前需要先经过铬矿选矿处理,以减轻对管道和高压釜的磨损.目前瑞木红土矿项目选矿得到的铬铁矿精矿其铬铁质量分数比(w(Cr2O3)/w(Fe O))仅为2.3,不能满足冶金级铬铁矿的要求.针对瑞木红土矿项目摇床分选所得的铬铁矿粗精矿开展了工艺矿物学和磁选提高铬铁质量分数比的研究.筛分实验和矿物提纯实验结果表明,去除细颗粒矿物以及分离脉石矿物是提高铬铁矿铬铁质量分数比的有效途径.对筛分后的+0.074 mm的粗精矿进行磁选分离,所得到的铬铁矿精矿铬铁质量分数比为2.59,铬回收率为63.89%.     

Unsaturated flow and solute transport in a porous column using spherical ore particles

This paper dealt with the development of a two-dimensional (2D) mathematical model for column leaching and confirmed the important simulation parameters through experiment. The unsaturated state of the variably saturated flow column and the solute transport of copper ions were studied during leaching. The fluid flow problem was handled using the Richards equation on the premise of an ambient pressure column air, where the van Genuchten formulas were applied to define the nonlinear relationships of pressure head with the retention and permeability properties. The ore column permeability test gave a varied hydraulic conductivity, which was analyzed in the model. In the solute transport problem, the copper ion concentration was solved using the advection-diffusion-reaction equation whose reaction term was determined by the joint analysis of experimental copper leaching rate and the shrinking core model. Particle- and column-scale leaching tests were carried out to illustrate the difference and connection of copper extraction in both processes. This fluid flow and solute transport coupled model was determined through the finite element method using the numerical simulation software, COMSOL Multiphysics.     

铬矿熔融还原动力学

考察了渣碱度、渣中Ａｌ２Ｏ３含量以及温度对铬矿被固体碳还原反应的影响，得到渣碱度在０．８～１．５的范围内、渣碱度为１．５时，铁液中最终铬含量最高；随着渣中Ａｌ２Ｏ３含量的增加，铬矿的初期反应速率明显降低，但对铁液中的平衡铬含量无明显影响．初期零级反应的表观活化能为３１６ｋＪ／ｍｏｌ．在确定反应控制环节时，利用了改变界面反应条件这一新方法，结合实验分析得到铬矿的还原是由铬矿在渣中的行为及界面反应联合控制     

熔融还原法铬合金的直接合金化

采用三种结构的坩埚对不同还原条件下铬矿的熔融还原动力学进行了实验研究，确定了应用熔融还原法实现了含铬合金钢直接合金化时渣中存在固体碳的必要性，针对实际生产进行工艺分析，提出了集还原和精于一身的ＡＯＤ法是进行熔融还原法含铬合金钢的直接合金化的最佳装置之一，认为这种短而灵活的工艺流程非常适应于中小规模生产。     

盐酸体系中二氧化锰浸出方铅矿的研究

在盐酸溶液中,用二氧化锰浸出方铅矿精矿制备氯化铅,并考察操作参数对铅浸出率的影响。研究结果表明盐酸体系中二氧化锰浸出方铅矿的最佳操作条件如下:搅拌速率为500 r/min,反应体系中总液体与总固体质量比为10,二氧化锰与方铅矿精矿质量比为1.3,反应时间为60 min,反应温度为80℃,盐酸浓度为3 mol/L,氯化钠质量浓度为250 g/L;在此最佳操作条件下,方铅矿精矿中的铅浸出率在99.5%以上,氯化铅产物纯度在99.6%以上。     

钴镍渣中锌的溶出动力学研究

基于硫酸选择性溶出钴镍渣中金属锌的“腐蚀微电池”作用本质,推导了其溶出反应的动力学方程．建立了钴镍渣中金属锌溶出反应的实验装置,获取了反应温度为15℃时溶出的氢气体积随时间变化的数据．以所建立的动力学方程结合实验数据进行计算,结果表明,硫酸选择性溶出钴镍渣中金属锌并生成氢气的反应,在室温15℃条件下具有一级反应的动力学特征,其表观反应速率常数k＊=0．5617min^-1.     

Activation pretreatment of limonitic laterite ores by alkali-roasting using NaOH

Activation pretreatment of Cr-containing limonitic laterite ores by NaOH roasting to remove Cr, Al, and Si, as well as its effect on Ni and Co extraction in the subsequent pressure acid leaching process was investigated. Characterization results of X-ray diffraction (XRD) and scanning electron microscopy/X-ray energy dispersive spectroscopy (SEM/XEDS) show that goethite is the major Ni-bearing mineral, and chromite is the minor one. Experimental results show that the leaching rates of Cr, Al, and Si are 95.6wt%, 83.8wt%, and 40.1wt%, respectively, under the optimal alkali-roasting conditions. Compared with the direct pressure acid leaching of laterite ores, the leaching rates of Ni and Co increase from 80.1wt% to 96.9wt% and 70.2wt% to 95.1wt% after pretreatment, respectively. Meanwhile, the grade of acid leaching iron residues increases from 54.4wt% to 62.5wt%, and these residues with low Cr content are more suitable raw materials for iron making.     

Preparation of manganese sulfate from low-grade manganese carbonate ores by sulfuric acid leaching

In this study, a method for preparing pure manganese sulfate from low-grade ores with a granule mean size of 0.47 mm by direct acid leaching was developed. The effects of the types of leaching agents, sulfuric acid concentration, reaction temperature, and agitation rate on the leaching efficiency of manganese were investigated. We observed that sulfuric acid used as a leaching agent provides a similar leaching efficiency of manganese and superior selectivity against calcium compared to hydrochloric acid. The optimal leaching conditions in sulfuric acid media were determined; under the optimal conditions, the leaching efficiencies of Mn and Ca were 92.42% and 9.61%, respectively. Moreover, the kinetics of manganese leaching indicated that the leaching follows the diffusion-controlled model with an apparent activation energy of 12.28 kJ·mol-1. The purification conditions of the leaching solution were also discussed. The results show that manganese dioxide is a suitable oxidant of ferrous ions and sodium dimethyldithiocarbamate is an effective precipitant of heavy metals. Finally, through chemical analysis and X-ray diffraction analysis, the obtained product was determined to contain 98% of MnSO₄·H₂O.     

斑铜矿在酸性溶液中的浸出动力学行为

以斑铜矿为研究对象,在H₂SO₄酸性体系中,以NaS₂O₈为氧化剂,详细考察浸出时间、温度、矿物尺寸、液固比、H₂SO₄浓度和NaS₂O₈浓度对铜浸出率的影响.浸出行为表明,斑铜矿浸出动力学行为符合固体膜层的界面传质和扩散的混合控制,表观反应活化能为33.97 kJ/mol,浸出动力学方程为（ln(1-x)）/3-1+(1-x)^-1/3=k_mt.     

高铟闪锌矿在氧压酸浸中铟浸出动力学的研究

铟是一种重要的多用途战略金属,具有较高的工业应用价值,但无独立可供开采的矿床,常伴生于铅锌等硫化矿中.因此,本文在传统电加热条件下进行了高铟闪锌矿氧压酸浸过程中铟浸出动力学实验的研究.结果表明:采用“有固态产物层的液-固相浸出反应动力学模型”对铟浸出动力学进行了研究,可知其浸出速率受到界面化学反应控制,其表观活化能为69.735kJ/mol,以及高铟闪锌矿氧压酸浸过程中铟浸出率随粒度减小、初始酸度增大、氧分压增大、浸出温度增大而增大.