The oxidation behavior of unactivated and mechanically activated sphalerite

The oxidation behaviors of unactivated and mechanically activated sphalerites were investigated using the thermogravimetry method (TG) in flowing highly pure oxygen at the heating rate of 10 K min⁻¹. It is found that the remaining mass between 400 and 873 K in the TG curves of mechanically activated sphalerites rises with increasing grinding time. The difference in oxidation reactivity of unactivated and mechanically activated sphalerites was also discussed. The specific granulometric surface area (S _G), the structural disorder, and the content of elemental sulfur of unactivated and mechanically activated sphalerites were determined by X-ray diffraction (XRD) laser particle size analysis, X-ray diffraction, and the gravimetric method, respectively. The results show that the specific granulometric surface areas of mechanically activated sphalerites remain almost constant after a certain grinding period. The elemental sulfur contents of unactivated and mechanically activated sphalerites were determined to be 0.5 mg/g, and the lattice distortions (ɛ) increase but the crystallite sizes (D) decrease with increasing grinding time. All the results imply that the mass increase between 400 and 873 K in the TG curves of mechanically activated sphalerites depends mainly on the increase of lattice distortions (ɛ) and the decrease of the crystallite sizes (D) with increasing grinding time. It was concluded that TG is a useful method for characterizing mechanically activated sphalerites.     

Trace Elements and Rare Earth Elements of Sulfide Minerals in the Tianqiao Pb-Zn Ore Deposit, Guizhou Province, China

Trace elements and rare earth elements(REE)of the sulfide minerals were determined by inductively-coupled plasma mass spectrometry.The results indicate that V,Cu,Sn,Ga,Cd,In,and Se are concentrated in sphalerite,Sb,As,Ge,and Ti are concentrated in galena,and almost all trace elements in pyrite are low.The Ga and Cd contents in the light-yellow sphalerites are higher than that in the brown and the black sphalerites.The contents of Ge,Ti,In,and Se in brown sphalerites are higher than that in light-yellow sphalerites and black sphalerites.It shows that REE concentrations are higher in pyrite than in sphalerite,and galena.In sphalerites,the REE concentration decreases from light-yellow sphalerites,brown sphalerites,to black sphalerites.The ratios of Ga/In are more than 10,and Co/Ni are less than 1 in the studied sphalerites and pyrites,respectively,indicating that the genesis of the Tianqiao Pb-Zn ore deposit might belong to sedimentary-reformed genesis associated with hydrothermal genesis.The relationship between LnGa and Lnln in sphalerite,and between LnBi and LnSb in galena,indicates that the Tianqiao Pb-Zn ore deposit might belong to sedimentary-reformed genesis.Based on the chondrite-normalized REE patterns,δEu is a negative anomaly(0.13-0.88),andδCe does not show obvious anomaly(0.88-1.31); all the samples have low total REE concentrations(<3ppm)and a wide range of light rare earth element/high rare earth element ratios(1.12-12.35).These results indicate that the ore-forming fluids occur under a reducing environment.Comparison REE compositions and parameters of sphalerites,galenas,pyrites,ores,altered dolostone rocks,strata carbonates,and the pyrite from Lower Carboniferous Datang Formation showed that the ore-forming fluids might come from polycomponent systems,that is,different chronostratigraphic units could make an important contribution to the ore-forming fluids.Combined with the tectonic setting and previous isotopic geochemistry evidence,we conclude that the ore-deposit genesis is hydrothermal,sedimentary reformed,with multisources characteristics of ore-forming fluids.     

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.     

The thermal behavior of mechanically activated galena by thermogravimetry analysis

The thermal decompositions of mechanically activated and nonactivated galenas were studied by thermogravimetry analysis (TGA) at the heating rate of 10 K min⁻¹ in argon. Results indicate that the initial temperature of thermal decomposition (abbreviated as T _di) in the TGA curves for different galenas decreases gradually with increased grinding time. The specific granulometric surface area (S _G), the structural disorder, and the content of elemental sulfur of mechanically activated galenas were analyzed by an X-ray diffraction (XRD) laser particle-size analyzer, XRD analysis, and the gravimetric method, respectively, which shows that the specific granulometric surface area of mechanically activated galenas remains almost constant after a certain grinding time, but the lattice distortions (ε) rise, the crystallite sizes (D) decrease, and the elemental sulfur contents of mechanically activated galenas increase with increased grinding time. The results imply that the decrease of the initial temperature of thermal decomposition in the TGA curves for mechanically activated galenas is mainly caused by the increase of lattice distortions, and the formation of new dangling bonds resulted from the production of elemental sulfur of mechanically activated galenas with increased grinding time. Finally, the differences in the thermal-decomposition reactivity between nonactivated and mechanically activated galenas were also discussed.     

The thermal behavior of mechanically activated galena by thermogravimetry analysis

The thermal decompositions of mechanically activated and nonactivated galenas were studied by thermogravimetry analysis (TGA) at the heating rate of 10 K min⁻¹ in argon. Results indicate that the initial temperature of thermal decomposition (abbreviated as T _di ) in the TGA curves for different galenas decreases gradually with increased grinding time. The specific granulometric surface area (S _G ), the structural disorder, and the content of elemental sulfur of mechanically activated galenas were analyzed by an X-ray diffraction (XRD) laser particle-size analyzer, XRD analysis, and the gravimetric method, respectively, which shows that the specific granulometric surface area of mechanically activated galenas remains almost constant after a certain grinding time, but the lattice distortions (ɛ) rise, the crystallite sizes (D) decrease, and the elemental sulfur contents of mechanically activated galenas increase with increased grinding time. The results imply that the decrease of the initial temperature of thermal decomposition in the TGA curves for mechanically activated galenas is mainly caused by the increase of lattice distortions, and the formation of new dangling bonds resulted from the production of elemental sulfur of mechanically activated galenas with increased grinding time. Finally, the differences in the thermal-decomposition reactivity between nonactivated and mechanically activated galenas were also 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%。     

某金矿石中金的氰化浸出研究

某矿石以石英脉型和石英-黄铁矿型矿石为主。金属矿物以黄铁矿为主，其次为黄铜矿、闪锌矿；氧化矿石中的黄铁矿已赤铁矿化和磁铁矿化。金矿物以自然金为主，矿金品位为4．46g／t，试验在适宜条件下，获得了金浸出率为94．62%，炭吸附率99．99％，的较好指标。     

Pressure Leaching Kinetics of Multimetallic Sulphide Concentrates in H2SO4 + O2 Solution

Abstract

A multimetallic sulphide concentrate containing sphalerite, galena, chalcopyrite and silver in the matrix of pyrite was decomposed at elevated temperature and oxygen pressures in dilute sulphuric acid solutions for sufficient residence time to yield 95% of the zinc in the pregnant solution while most of the lead and silver remained in the residue together with most of the pyrite. The selective leaching process appeared to follow the diffusion controlled mechanism. The effects of concentration of the leachant, temperature and time of leaching, particle size, oxygen pressure and agitation on the leaching process were investigated. Results indicate the prospect of extracting not only all the metals but also appreciable amounts of elemental sulphur under optimized experimental conditions.     

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。     

Oxidative acid leaching of mechanically activated sphalerite

The pressure leaching kinetics of mechanically activated sphalerite was investigated in this work. X-ray diffraction and scanning electron microscopy were used to characterise the influences of crystalline structure and morphology, respectively. A laser particle size analyser and specific surface area tester were used to determine the particle size and specific surface area, respectively. Compared to the non-activated sample, the activated samples demonstrated distinct physicochemical properties with higher reaction efficiencies and increased Zn recovery ratios. The activation energy of sphalerite decreased from 69.96 to 45.91, 45.11, and 44.44?kJ?mol^?1 as the activation time increased from 0 to 30, 60, and 120?min, respectively. The reaction orders for the H₂SO₄ solutions of the sphalerite samples activated for 0, 30, 60, and 120?min were 1.832, 1.247, 1.214, and 1.085, respectively, which indicated that the dependency of the sphalerite leaching process on H₂SO₄ could be reduced by means of mechanical activation.     

Effects of Mechanical Activation on the HCl Leaching Behavior of Titanaugite,Ilmenite, and Their Mixtures

Structural changes of mechanically activated titanaugite were investigated systematically using X-ray diffraction, particle size analysis, and scanning electron microscopy. The hydrochloric acid leaching behavior of mechanically activated titanaugite and ilmenite single minerals and their mixtures also was studied. The results show that with increasing milling time, the crystallite size, lattice strain, and particle size changed continuously. Mechanical activation evidently improved the leaching reactivity of titanaugite and ilmenite with 20 wt pct HCl at 378 K (105 °C). The leaching behavior of ilmenite was promoted at the initial stage and then was inhibited when mixed with a mass ratio of titanaugite to ilmenite of 1:1. When the mass ratio of titanaugite to ilmenite decreased to 1:9, the leaching of titanaugite was promoted, whereas the leaching of ilmenite was inhibited throughout the whole process. The leaching inhibition of ilmenite is related to the formation of hydrous silicon dioxide from the dissolution of titanaugite.     

A kinetic study on the pressure leaching of sphalerite

The dissolution of sphalerite (ZnS) in sulfuric acid solution under oxygen pressure was investigated. Effects of temperature, percent solids, agitation, sample size, oxygen partial pressure and foreign ions were evaluated. The effect of hydrogen pretreatment on sphalerite leaching rate was also examined. Leaching of sphalerite at 90°C and 150 psi oxygen pressure was found to occur at a constant rate. This rate was determined from the experimental data observed under the different leaching conditions mentioned above. The constant leaching rate was attributed to the chemical reaction occurring on the surface of the flat-plate type sphalerite sample. The rate-controlling step of the reaction was determined to be the oxidation of hydrogen sulfide to elemental sulfur. Oxidation of hydrogen sulfide was studied through the addition of iron and through the observation of the change in iron concentration during leaching. The oxidation was concluded to be by reaction with ferric ion rather than by direct oxygen oxidation. Leaching tests run with samples pretreated with hydrogen do not show any increase in the rate of zinc extraction. M. T. HEPWORTH, formerly with University of Denver.     

Use of X-ray diffraction in a study of ammonia leaching of multimetal sulfides

X-ray diffraction has been used to study the changes in mineralogy that occur during ammonia leaching of sulfide minerals and complex bulk sulfide concentrates. Leaching results in high extraction rates (>90 pct) of copper from chalcopyrite, zinc from sphalerite, and lead from galena. However, under experimental leaching conditions (temperature, 115 °C to 135 °C; par-tial pressure of oxygen, 1.5 kg/cm²; pH ∼ 10.0), the pyrite grains are practically inert. Ap-parently, the amount of pyrite in leach residue is constant in absolute terms. However, its relative percentage changes because the amount of copper and zinc minerals is reduced in the leach residue during progressive leaching. The products formed during the leaching reaction, such as goethite and lead sulfate, tend to increase the weight of the leach residue, and thus the relative weight of pyrite remains nearly unchanged. The ratios of selected line pair intensities of pyrite lines and characteristic (selected) lines of chalcopyrite, sphalerite, and galena are used to establish the oxidative ammonia leaching kinetics of Cu-Zn-Pb bulk concentrates. That is, the variation in the line pair intensity ratios, with time, correlates with the changes in the el-emental concentrations in the leach liquor.     

A kinetic study on nonoxidative dissolution of sphalerite in aqueous hydrochloric acid solutions

The nonoxidative leaching of sphalerite in aqueous acidic solutions was studied from a kinetic point of view. Also the selective nonoxidation leaching in a hydrochloric acid solution containing a large amount of sodium chloride was examined for a Pb-Zn sulfide bulk concentrate. The dissolution rates of sphalerites from five different mines appeared to be controlled by a chemical reaction on the surface of sphalerite. The dissolution rate of sphalerite is of the first order with respect to the hydrogen ion activity of the solutions. It is also considerably affected by the iron content of the sphalerite sample; a linear relationship was observed between iron content of the sphalerite and its dissolution rate. The addition of sodium chloride to the hydrochloric acid solutions greatly enhanced dissolution rates. Compared to the dissolution rates of galena, which were reported in a previous paper, the dissolution rates of sphalerite were found to be far slower. The difference in the dissolution rates between these two minerals becomes greater with the addition of sodium chloride to the hydrchloric acid solutions. Based on these findings, the selective leaching of Pb-Zn bulk concentrate in a hydrochloric acid solution containing a large amount of sodium chloride was examined. The experimental results clearly showed that the galena was selectively leached, leaving a residue of sphalerite. NORIO MISAKI formerly Graduate student, Kyoto University     

机械活化强化铌钽矿碱性水热体系浸出

针对现行铌钽矿HF酸处理工艺氟污染严重的问题,提出以KOH溶液替代高毒性HF介质的铌钽矿碱性水热体系浸出新方法,研究了铌钽矿在KOH碱性水热体系浸出规律.结果表明,在KOH质量分数50%范围内,KOH质量分数和反应温度的提高会促进铌钽矿分解生成可溶性六铌(钽)酸钾,但过高的KOH质量分数和反应温度会使可溶性六铌(钽)酸钾向不溶性偏铌(钽)酸钾转化,造成铌、钽浸出率的下降.在KOH质量分数35%、反应温度200℃、碱矿质量比4:1以及反应时间2 h的最佳浸出条件下,铌和钽浸出率仅为18.73%和9.4%;通过机械活化对铌钽矿进行预处理后,铌和钽浸出率可大幅度提高至95%和60%,说明机械活化可显著强化铌钽矿碱性水热浸出过程.铌钽矿经机械活化后,矿物粒度减小,比表面积增加,晶格畸变增大,无定形化程度增加,内部缺陷程度增加,矿物的反应活性大大增加,铌钽矿的浸出率显著提高.     

西秦岭寨上特大型金矿床黄铁矿特征及其含金性研究

寨上金矿中黄铁矿是主要的载金矿物之一。围岩中黄铁矿呈草莓状、莓球状、圆球状和立方体等晶形,颗粒相对较细小。矿石中黄铁矿呈立方体、五角十二面体、他形粒状及细网脉状,颗粒相对较粗。寨上金矿黄铁矿化学成分总体呈贫铁ｗ（Fe）=45.98%,贫硫w（S）= 51.69%,As、Sb等替代S,Co、Ni、Ag等替代Fe,Au呈独立矿物形式存在于黄铁矿中。草莓状和立方体黄铁矿含金性较差,他形粒状、细脉状及五角十二面黄铁矿含金性较好。不同晶形黄铁矿中Au与As呈负相关性。具有增生环带铁矿的第一 、三、五环带含Au、As较高,而内核、第二、四、六环带中Au、As较低,Au与As呈正相关性。     

Leaching studies of chalcopyrite and sphalerite with hypochlorous acid

Laboratory studies have been conducted on the leaching of chalcopyrite and sphalerite with hypochlorous acid. The effects of stirring speed, temperature, pH, and hypochlorous acid concentration on the leaching rates have been determined. In addition, the leaching mechanisms have been resolved by analyzing the concentrations of the reaction products. It has been found that more than 90 pct extraction of both chalcopyrite and sphalerite can be achieved in one hour using less than 0.3 molar hypochlorous acid at room temperature. The primary leach products of chalcopyrite and sphalerite were sulfur and sulfate in the mole ratios of 1 to 1 and 2 to 1, respectively. A mixed kinetic model was applied to explain the leaching rates of chalcopyrite while a diffusion model was applied to explain the leaching rates of sphalerite. The mixed kinetic model involved steady-state diffusion of hypochlorous acid through the sulfur layer by a chemical reaction at the reaction interface. Good agreement between these models and the leaching rates of both minerals was obtained.     

氧压浸出处理低铁闪锌矿

以低铁闪锌矿精矿为原料,采用氧压浸出技术进行处理。绘制了150℃、1.0 MPa的ZnS-H2O系电位-pH图。通过单因素试验确定各因素的影响趋势,采用ICP、XRD、XRF和BET等检测方法对浸出液和浸出渣进行分析表征,确定最佳浸出条件为:精矿粒度-0.075 mm～+0.055 mm、浸出温度150℃、氧分压0.8 MPa、初酸浓度15%、浸出时间90 min、浸出液固比6∶1～8∶1、搅拌转速500 r/min、添加剂用量1.0%。在此条件下,锌浸出率在97%以上,硫转化率达到90%,实现了精矿中锌的充分浸出与渣中元素硫的富集。     

The Dissolution of Sphalerite in Ferric Chloride Solutions

The kinetics of dissolution of both sintered sphalerite disks and untreated sphalerite particles in ferric chloride-hydrochloric acid solutions have been investigated. Over the temperature interval 25 to 100°C, the dissolution occurred according to a linear rate law and with an associated apparent activation energy of about 10 kcal/mole. Most of the oxidized sulfide ion reported as elemental sulfur in the leach residues. The leaching rate was independent of the disk rotation speed and this fact, together with various hydrodynamic calculations, indicated that the reaction was chemically controlled. The dissolution rate increased as the 0.36 power of the ferric chloride concentration and it also increased substantially in the presence of dissolved CuCl₂. The accumulation of the ferrous chloride reaction product severely retarded the leaching reaction, but the presence of dissolved zinc chloride only slightly impeded it. The leaching rate was relatively insensitive to low levels of HC1 (>1 M), but increased dramatically at higher acid concentrations because of direct acid attack of the ZnS.     

Galvanic interaction between chalcopyrite and pyrite during bacterial leaching of low-grade waste

The bacterial leaching of a low-grade chalcopyrite waste rock in a lixiviant containing thermophilic, Sulfolobus-like microorganisms at 60°C and a lixiviant containing Thiobacillus ferrooxidans at 28°C has been compared with the leaching in sterile lixiviant in terms of copper solubilized in elapsed time and the conversion of $\text{Fe}{}^{\mathrm{3+}}\text{Fe}{}^{\mathrm{2+}}$. Bacterial action has been shown to drastically increase the ratio $\text{Fe}{}^{\mathrm{3+}}\text{Fe}{}^{\mathrm{2+}}$ with elapsed time of leaching. Direct observations of the associated pyrite and chalcopyrite surface corrosion, utilizing scanning electron microscopy, showed that during the leaching of these sulfides as separate, non-contacting phases, the pyrite corroded more rapidly than the chalcopyrite in both sterile and inoculated media. This effect was more pronounced at elevated temperature and in the presence of bacteria. When the pyrite and chalcopyrite were in contact, the resulting galvanic interaction caused the chalcopyrite to corrode more rapidly than the pyrite, which was effectively passivated. The leaching of chalcopyrite is thereby enhanced in contact with pyrite. This effect is accelerated in the presence of bacteria. The corrosion of chalcopyrite was also markedly enhanced as a result of the oxidation of elemental sulfur (formed during the reaction) to sulfuric acid. This reaction was also accelerated by bacterial catalysis. The important implications of the enhanced chalcopyrite corrosion by galvanic interaction in the leaching of low-grade chalcopyrite waste and other galvanic-contact regimes involving metal sulfides are identified and discussed.