高硫铝土矿脱硫精矿拜耳法溶出氧化铝试验研究

研究了用拜耳工艺从高硫铝矿脱硫精矿中溶出铝。结果表明,拜耳工艺溶出过程中,以黄铁矿形式存在于脱硫精矿中的硫会随黄铁矿的溶解进入溶液;在溶解温度265℃、溶解时间60 min、循环母液Na_2O_k质量浓度235 g/L、分子比1.45、石灰用量为矿石质量7.5%条件下,铝土矿脱硫精矿中的氧化铝的相对溶出率为97.5%,硫溶出率为19.5%。     

低品位高硫铝土矿低温焙烧脱硫研究

为解决低品位高硫铝土矿工业应用中硫含量过高及溶出问题,采用低温焙烧技术路线,考察焙烧温度、焙烧时间及矿石粒径对焙烧脱硫的影响。结果表明,最佳焙烧脱硫条件为:焙烧温度650℃、焙烧时间180s、矿石粒径48μm。在该条件下铝土矿硫脱除率达到75.83%,焙砂中硫含量为0.29%。相同条件下焙烧矿氧化铝相对溶出率为97.63%,较原矿提高了7.32个百分点。铝土矿中硫主要以黄铁矿形式存在,在焙烧过程黄铁矿优先于一水铝石与高岭石反应。     

拜耳法高温溶出工艺实验研究

针对我国铝土矿高硅高铝,溶出困难的特点,着重研究碱法即拜耳法高温溶出铝土矿制备铝酸钠溶液的工艺过程。分别选用某铝厂母液和碱溶液浸出铝土矿,改变苛性碱浓度、温度、时间、液固比和矿石粒度,分析各因素对铝土矿中Al2O3的溶出率的影响,从而得到最佳的溶出条件。     

高碳铝土矿焙烧预处理及焙烧矿的溶出试验研究

对高碳铝土矿进行了焙烧预处理和溶出试验研究。试验结果表明:在温度600℃条件下焙烧20min,焙烧矿中的总碳含量可降低至0.064%,总碳的脱除率可达到97.17%;矿石中几乎全部的硫保留在焙烧矿中,焙烧过程不增加烟气中SO_2排放。在溶出温度260℃、石灰添加量10%及溶出液αK 1.40左右的条件下,焙烧矿的溶出效果良好:氧化铝溶出率达到76.77%,溶出赤泥A/S 1.22,溶出赤泥N/S 0.52。在焙烧矿溶出过程中,矿石中的硫绝大多数进入赤泥,仅有不到5%进入溶液,焙烧矿中的硫对氧化铝生产过程影响不大。     

优化条件下氧化锌对高硫铝土矿溶出过程脱硫的影响

研究在优化条件下添加氧化锌对一水硬铝石型高硫铝土矿溶出过程脱硫的影响。结果表明,优化溶出条件下高硫铝土矿溶出过程中加入氧化锌后,硫溶出率随氧化锌加入量增加而降低,氧化铝溶出率基本不变。溶出液中S2-含量随氧化锌加入量增加而降低,其他价态硫不随氧化锌加入量变化。优化溶出条件下,不同硫含量矿样在添加氧化锌后溶出的氧化铝溶出率基本不变,而硫溶出率随着矿样硫含量的增加,不断增加。添加10%氧化锌适合处理硫含量在1.373%以下的高硫铝土矿。     

老挝铝土矿中铁矿物微观结构及反应特性的研究

利用扫描电镜及能谱仪对铝土矿中铁矿物微观结构及成分进行分析,着重研究铝土矿中赤铁矿、针铁矿、钛铁矿等矿物的存在方式及分布特征。结果表明,针铁矿较多时明显影响赤泥的沉降速度,碳加入量大于10%及高温溶出能显著改善老挝矿的溶出效果,赤铁矿不与矿石中各组分和铝酸的溶液反应而直接进入赤泥中。     

铝土矿中S2-含量的测定

依据拜耳法生产氧化铝高压溶出原理,同时结合铝土矿中的以黄铁矿、褐铁矿形式存在的硫在280℃高温高压条件下可与氢氧化钠作用生成硫化钠进入溶液的实验条件,在溶出液中加入盐酸酸化,生成硫化氢气体用镉盐溶液吸收,在吸收液中,加入过量的碘标准溶液和盐酸与硫化氢反应.过量的碘用硫代硫酸钠标准溶液滴定,以求出矿中S2-的含量.     

拜耳法氧化铝生产过程中锂的富集机制研究

研究了拜耳法氧化铝生产过程中锂的富集机制。结果表明,在拜耳法氧化铝生产工艺中,铝土矿中约有80%金属锂在高压溶出过程中以铝酸锂的形式进入铝酸钠溶液,后经晶种分解全部进入结晶氢氧化铝中,在氢氧化铝的高温煅烧过程中,因升华作用损失约25%的金属锂,其余以氧化物形式富集在氧化铝制品中,其含量随着入磨铝土矿中金属锂含量的增加而增加、随铝土矿A/S比的增加而降低。     

高硫铝土矿微波焙烧脱硫预处理及焙烧矿高压溶出性能

采用微波焙烧方式研究高硫铝土矿的脱硫效果,并对焙烧脱硫后的焙烧矿进行拜耳法溶出,研究了微波焙烧条件对氧化铝溶出率的影响。结果表明,高硫铝土矿微波焙烧脱硫,焙烧温度相较于焙烧时间对脱硫率的影响更为显著,焙烧温度由100 ℃升高到600 ℃,脱硫率可平均提高约30%,而焙烧时间由2 min延长至20 min,脱硫率仅平均提高12%。在600 ℃焙烧20 min,可将铝土矿全硫含量由3.875%脱除至0.223 5%,脱硫率达到95.11%。同时,微波焙烧温度对氧化铝的溶出率影响也较显著,随着微波焙烧温度升高,氧化铝的相对溶出率有先提高后下降的趋势,微波焙烧温度为400 ℃时,焙烧矿的氧化铝相对溶出率达到最大,为94.77%;当焙烧温度高于400 ℃时,焙烧矿会出现大量刚玉（Al₂O₃）相,是导致氧化铝相对溶出率下降的主要因素。      

K+对拜耳法溶出过程中含钾铝土矿反应行为的影响

用不同K~+浓度的铝酸钠溶液进行了含钾铝土矿的拜耳法溶出试验和溶液脱硅试验。结果表明,在30.19～301.94g/L内,溶液中K~+浓度的变化对氧化铝溶出率和溶出赤泥N/S的影响较小;随着溶液中K~+浓度的升高,铝土矿中K_2O的表观溶出率显著降低,但无法完全阻止K元素在溶出过程中进入溶液。在溶液中K~+浓度≤155.28g/L条件下,K~+取代Na~+进入钠硅渣晶格的难度大,工厂溶液中K~+的平衡浓度预计会远高于当前的水平。应用含钾铝土矿生产的企业必须采取除钾工艺措施才能有效控制生产系统中钾含量的升高。     

A Kinetic study of leaching of coal pyrite with nitric acid

The leaching of coal pyrite with nitric acid has been investigated. The temperature ranged from 313 to 363 K, and the concentration of nitric acid was varied from 0.154 to 1.54 mol/l. A coal sample of 50 grams was leached in a reactor containing 500 ml of solution in an open system. It was observed that the leaching reaction could remove 47 pct of the pyrite sulfur in seven minutes and 88 pct in 30 minutes at 343 K with 1.54 mol/l of nitric acid. The reaction order with respect to hydrogen and nitrate ion activity was found to be first order. The activation energy for the initial stage of the reaction was determined to be 14.7 K cal/mol (61.5 kJ/mol). A mathematical model was developed on the basis of mixed kinetics (reaction zone model) to explain the leaching rates. Good agreement between experimental rate data and predicted rate curves by the developed model was obtained. Ultimate analysis was used to determine the extent of nitration of the leached coal. This nitration was found to be insensitive to the reaction temperature and acidity of the solution.     

铝酸钠溶液中钡盐脱硫热力学分析

对铝酸钠溶液中钡盐脱硫反应进行热力学计算,分析脱硫过程中硫碱和碳碱在铝酸钠溶液中的行为。结果表明,增加温度有利于脱硫和脱碳反应的进行,尽量降低碳碱含量,有利于硫的脱除;脱硫过程应选择适当的脱硫率和终了硫碱及碳碱浓度;钡盐添加率增大有利于脱硫,但添加率过高会使脱硫剂反应不完全。     

镍钼矿氧压水浸过程铁和硫的转化溶解行为模拟研究

针对镍钼矿中硫铁矿的氧压水浸行为,以硫铁矿为研究对象,研究压力场下初始硫酸浓度、温度、氧分压、矿物粒度对硫铁矿氧压水浸行为的影响。结果表明:硫铁矿氧压水浸过程中,铁元素主要以离子形式存在溶液中,少部分以三氧化二铁、铁矾留在渣中;硫元素在整个反应过程中主要以硫酸根的形式存在溶液中,少部分以单质硫的形式存在渣中;外加初始酸的条件下,反应初期耗酸量大于成酸量为耗酸反应,反应中后期成酸量大于耗酸量为成酸反应;不加初始酸的条件下为成酸反应。     

Effect of aging conditions on the leaching of mechanically activated pyrite and sphalerite

The leaching of mechanically activated pyrite and sphalerite exposed to nitrogen (99.999 vol pct) or air at ambient temperature or 573 K was investigated. The results indicate that at the same leaching time, the iron-leaching ratio of mechanically activated pyrite or sphalerite aged in nitrogen at both ambient temperature and 573 K decreases slightly with increasing aging time and remains constant after a certain aging period. The iron-leaching ratio of mechanically activated pyrite exposed to ambient air varies with the exposure period. But, at the same leaching time, the zinc-leaching ratio of mechanically activated sphalerite aged at ambient temperature does not change with the aging atmosphere. The structures of mechanically activated pyrite and sphalerite after being aged were determined. The specific granulometric surface area of mechanically activated pyrite and sphalerite decreases with increasing aging time, but keeps constant after a certain aging period. The X-ray diffraction patterns of mechanically activated pyrites aged in nitrogen do not change with aging time; neither do the X-ray diffraction patterns of mechanically activated sphalerites aged either in air or in nitrogen. For mechanically activated pyrite exposed to ambient air for 3 and 6 months, new phases were found. The lattice distortion and the elemental sulfur content of pyrite and sphalerite mechanically activated in nitrogen were also investigated. The results indicate that the elemental sulfur content of mechanically activated pyrite rises noticeably, and its lattice distortion (ε) rises slightly, with increasing grinding time. The elemental sulfur content of mechanically activated sphalerite remains constant at 0.5 mg elemental sulfur per gram of sphalerite, and its lattice-distortion ratio increases apparently with increasing grinding time. These observations provide further evidence for our opinion that the formation of dangling bonds on the surface of mechanically activated pyrites and the lattice distortion on the surface of mechanically activated sphalerites may mainly result in the enhancement of hydrometallurgical process for corresponding sulfide minerals.     

载金硫化物焙烧-自浸出过程研究

针对传统氧化焙烧-氰化浸金工艺环境污染严重的现状,采用焙烧-自浸出工艺提取载金硫化物中的金.研究焙烧温度、焙烧时间和试样量对单质硫转化率和金浸出率的影响,通过X射线衍射分析、扫描电镜观察、能谱分析等手段分析焙烧过程中载金硫化物中硫的物相转变规律.载金硫化物中黄铁矿发生热分解反应生成单质硫和磁黄铁矿,随焙烧温度的升高和焙烧时间的延长,黄铁矿的特征衍射峰强度逐渐减小直到消失,磁黄铁矿的特征衍射峰逐渐生成并增强,原本致密状的黄铁矿颗粒变得疏松多孔.50 g试样在氮气流量1 L·min-1、焙烧温度800℃、焙烧时间60 min的条件下,单质硫的转化率达到42.53%,金浸出率达到88.70%,实现载金硫化物的高效非氰浸出.      

Effect of suspension potential on the oxidation rate of copper concentrate in a sulfuric acid solution

A chalcopyrite concentrate containing 17 pct pyrite was oxidized in 1 mol/dm³ sulfuric acid solution at 90 °C (363.2 K). The suspension potential (Ptvs SCE, in the presence of Fe³⁺/Fe²⁺) was maintained constant in the range 0.30 to 0.65 V by controlled additions of KMnO₄ solution. The oxidation appeared to be under surface reaction control. The rate constant was nearly independent of total Fe concentration (0.01 to 0.5 mol/dm³), but increased rapidly with a rise in suspension potential until it reached a maximum at 0.40 to 0.43 V, after which there was marked decrease at around 0.45 V. Chalcopyrite in the concentrate was oxidized to form elemental sulfur over the whole of the suspension potential range, whereas the oxidation of pyrite took place only above 0.45 V and yielded sulfate ion. At 0.40 V the apparent activation energy was 47 kJ/mol. An analogy between the potential dependence of the rate and the Tafel correlation for an electrode process is discussed.     

硫铁矿-木炭湿法浸出高铁氧化锰矿的研究

针对两矿法浸出高铁氧化锰矿存在生成大量单质硫并覆盖在矿物颗粒表面,降低了反应速率的问题,研究采用在浸出过程中添加木炭粉的方法吸附单质硫以改善浸出效果。考察了木炭粉添加量、硫铁矿用量、硫酸浓度、浸出温度和浸出时间对高铁氧化锰矿中锰浸出率的影响。在高铁氧化锰矿用量10.0g、硫铁矿用量5.0g、木炭粉添加量0.1g、硫酸浓度1.36mol/L、浸出温度70℃和浸出时间4h的条件下,锰浸出率达到96.7%。     

Recovery of iron oxide concentrate from high-sulfur and low-grade pyrite cinder using an innovative beneficiating process

A high quality iron oxide concentrate, suitable as a feed for blast and electric reduction furnaces was recovered from high-sulfur and low-grade pyrite cinder. Pyrite cinder was treated with a hot strong alkali solution which dissolved most of the silica and alumina, leaving a solid residue and forming a precipitate which was an acid-soluble salt of aluminosilicate hydrate. The residue and precipitate were then treated with a diluted aqua regia to dissolve the precipitate and other impurities. Impurities such as the soluble silicates, aluminates and heavy metals can be extracted and produced high value-added products with several simple methods in later research. After analyzing the chemical composition and crystalline phase of raw material, the effects of different parameters on recovery efficiency of iron were carried out. The optimum reaction parameters were proposed as the following: melting at 200 °C for 1.0 h with 3.0 M NaOH in a liquid-solid ratio of 1.0:1.2 at atmospheric pressure, followed by leaching with aqua regia solution (3.0 vf.%) in a ratio of liquid-to-solid of 1.2:1.0 at room temperature for 1.5 h. In optimum parameters mentioned above, the raw residue only containing 38% Fe could be purified to about 65% and the recovery yield of Fe was 86%. Furthermore, the sulfur content of product could be reduced to 0.090% from 8.0%. To reveal the mechanism of this process, the phase transformation and microstructure of the process were studied by XRD and SEM with EDS.     

An Innovative Approach to Separate Iron Oxide Concentrate from High-sulfur and Low-grade Pyrite Cinders

High-sulfur and low-grade pyrite cinders are the waste products of sulfuric acid manufacturing plants.Many valuable components,such as iron oxide,are contained in pyrite cinders and difficult to be separated and purified just via the high temperature roasting process.Considering this,an innovative method including water-washing,aqua regia leaching,hydrothermal alkali activation and acid-washing was developed.And the effects of different parameters on recovery efficiency of iron oxide were systematically investigated.The optimum parameters were proposed as follows:water rinse-leaching at room temperature for 5-20 min,and melting at 160 ℃ for 2.0h with NaOH(concentration of 30mass%),followed by leaching with aqua regia solution(3.0vol.%)for 1.0h.After the treatment,the content of iron oxides increased from 54.3to 96.0mass% with the recovery rate exceeding 85%.Meanwhile,calcium sulphate was recovered as the high value-added products by alkali extraction liquid.Furthermore,the phase transformation and microstructure of the samples in the process were studied by physicochemical methods to reveal the separation mechanisms of different components in the pyrite cinders.     

黄铁矿对黄铜矿浸出的影响

常压条件下,黄铜矿浸出速率缓慢,难以达到理想的浸出效果。溶液中,黄铁矿与黄铜矿共同存在时,发生"原电池效应"可以促进黄铜矿溶解。探究了在H_2SO_4溶液、H_2SO_4-Fe_2(SO_4)_3溶液和H_2SO_4-H_2O_2溶液中,黄铁矿对黄铜矿浸出的影响。结果表明,黄铁矿可有效促进黄铜矿溶解,但浸出并不完全。在浸出过程中黄铜矿表面形成钝化层,影响物质转移与电子传递效果。钝化层的主要成分为缺金属硫化物和少量单质硫。