Collectorless flotation of chalcopyrite and sphalerite ores by using sodium sulfide

The flotation of chalcopyrite and sphalerite from copper and copper-zinc ores has been achieved without using thiol-type collectors. Typically, a sulfide ore sample is first treated with sodium sulfide either during grinding or during the preflotation conditioning period, and then the chalcopyrite is floated with frother alone. With a copper-zinc ore, sphalerite is subsequently floated from the chalcopyrite tailings by activating it with copper sulphate. Results of the collectorless flotation tests are comparable to those obtained by using thiol collectors. The mechanisms of selective collectorless flotation are discussed on the basis of differences in the solubilities of sulfide minerals.     

Flotation and adsorption studies of chalcopyrite with cupferron

Flotation tests were conducted in a Hallimond tube on chalcopyrite, with a collector system of cupferron and fuel oil. The reagent concentration, pH and conditioning time were studied as variables. The necessity of the fuel oil was verified by conducting experiments without it. Contact-angle measurements have been conducted by the captivebubble technique. From the results it was found that fuel oil is necessary to promote adhesion of the conditioned mineral particles to the air bubbles. Adsorption experiments were carried out in a column apparatus under similar conditions as in flotation, except for the addition of fuel oil. The adsorption density and flotability were high at weakly acidic range where the reagent complexes the metal ions effectively in an aqueous medium.     

The use of a new modifier,Kr6D,in differential sulphide flotation

The suitability of a new reagent, Kr6D, as a depressant for galena and sphalerite in a differential sulphide flotation stage has been tested. Small-scale laboratory flotation tests on pure sulphide minerals indicated that the reagent is capable of depressing both galena and sphalerite when used in small doses. At higher concentrations, chalcopyrite is also depressed. Single-stage batch-scale flotation tests have been carried out on bulk sulphide concentrates containing the three sulphide minerals. Kr6D has been compared with starch as a depressant both in the presence and in the absence of sulphur dioxide. In each case the new modifier has been shown to be more effective. When using sodium dichromate as a differential depressant in similar tests, it has been shown that the quantity necessary to achieve selectivity between chalcopyrite and galena may be considerably reduced if small quantities of Kr6D are added.     

Investigation of mechanism of ultrasound on coal flotation

Coal flotation studies were carried out in ultrasonically assisted flotation cells. Representative hard coal slime samples from Prosper-Haniel Coal Preparation Plant located in Bottrop, Ruhr Region of Germany were used for this purpose. A Wemco type flotation cell was fitted with transducers and tests were carried out at variable frequency and power. The reagent for coal flotation was Ekofol-440 with variable dosages during conventional and ultrasonic flotation experiments. The results showed that ultrasonic coal flotation yields more combustible recovery and lower ash values in concentrates than conventional flotation by using similar reagent dosages. These results are explained on the basis of efficient surface cleaning of the coal particles.     

Effect of oxidation potential and zinc sulphate on the separation of chalcopyrite from pyrite

The effects of oxidation potential (Eh) and zinc sulphate on the separation of chalcopyrite from pyrite were investigated at pH 9.0. The flotation recovery of these minerals is Eh dependent with maximum separation obtained at 275 mV SHE. Zinc sulphate addition improved this mineral separation at an Eh value of 275 mV by selectively depressing pyrite flotation. A different result was obtained at lower Eh values where zinc sulphate addition improved chalcopyrite flotation but had no or little effect on pyrite flotation. These opposite effects of zinc sulphate on mineral flotation were reconciled by examining the surface species of these minerals. The selective depression of pyrite flotation by zinc sulphate was also confirmed in the flotation of two copper ores.     

A laboratory study of the influence of sodium sulphide and oxygen on the collectorless flotation of chalcopyrite

The flotability of chalcopyrite in the absence of conventional collectors and its dependence on the oxidation-reduction state of the system has been determined in batch flotation tests on high-grade mineral both alone and mixed with quartz. It has been concluded that chalcopyrite is not floatable in reducing conditions either in the presence or absence of sodium sulphide but becomes floatable when oxygen is made available. No evidence was found to suggest that chalcopyrite ground in the near absence of oxygen is highly floatable.     

Study of galvanic interactions between pyrite and chalcopyrite in a flowing system: implications for the environment

When galvanic interactions between pyrite and chalcopyrite occur in solution, pyrite, with the higher rest potential, acts as a cathode and is protected whereas chalcopyrite, with the lower rest potential, acts as an anode and its oxidation is increased. In this work a three-electrode system was used to investigate the corrosion current density and mixed potential of a galvanic cell comprising a pyrite cathode and a chalcopyrite anode in a flowing system. The results showed that with increasing concentration of ferric ion in the solution, with increasing acidity, and with increasing flow rate of the solution, the corrosion current density increased and the mixed potential of the galvanic cell became more positive. These experimental results are of direct significance to the control of environmental pollution in mining activity. By using the galvanic model, mixed potential theory, and the Butler–Volmer equation, the experimental results were explained theoretically.     

内蒙古小西沟铅锌矿床矿石特征及可选性试验研究

小西沟锌铅矿床属于低温热液型矿床,矿石组成复杂,伴生铜和银,研究表明,该矿床矿石中的铅、锌、铜和银主要矿化元素以独立矿物产出,但部分黄铜矿与闪锌矿呈固溶体交生。根据矿石性质确定,该矿床矿石可采用混合浮选铜铅(铜、铅分离)—再浮选锌的工艺流程,通过试验获得符合标准的铜精矿、铅精矿和锌精矿,所用药剂没有环境污染,符合当前技术条件,可以开发利用。     

The natural flotability of chalcopyrite

In an extensive programme of batch flotation tests on mixtures of purified minerals, it was established that freshly ground chalcopyrite displayed natural flotability in an oxidising environment and non-flotability in a reducing environment. No rational hypothesis to account for this behaviour has emerged. Grinding in an iron mill produced strongly reducing conditions and consequently suppressed flotation which was restored subsequently by raising the potential of the pulp either by aeration or by the addition of oxidants. The coarse particle sizes recovered more slowly than other fractions. The type and addition of frother had a pronouced effect on the natural flotability, but no proven effect on hydrophobicity. There is some evidence that whilst these observations apply to chalcopyrite from several sources when floated from mixtures with quartz, chalcopyrite in real ore samples does not necessarily show the same flotation behaviour.     

Flotation of oxidized minerals of copper using a new synthetic chelating reagent as collector

A new synthetic reagent containing a mixed aliphatic-aromatic structure, with a hydrocarbon chain and an aminothiophenol chelating group, has proven to be an effective collector for the flotation of chrysocolla minerals. The flotation is optimum in the narrow pH range of 5.5 to 6, falls sharply at pH 5, and is moderate in the pH range 7 to 11. Infrared spectra indicate that copper aminothiophenolate chelates are formed on the surface of the chrysocolla under the conditions of maximum flotation.     

Interaction of thionocarbamate and thiourea collectors with sulphide minerals: a flotation and adsorption study

The ability of O-isopropyl-N-ethyl thionocarbamate (IPETC), O-isobutyl-N-ethoxycarbonyl thionocarbamate (IBECTC) and butyl ethoxycarbonyl thiourea (BECTU) collectors to increase the flotation of the sulphide minerals, chalcopyrite, galena and pyrite, has been studied. For each collector, the flotation characteristics of these minerals, flotation rate constant and flotation recovery maximum, have been calculated from the flotation data and compared as a function of pH and collector concentration. Overall, the flotation performance of these collectors is stronger for chalcopyrite than for galena and pyrite. Flotation increases with collector concentration and decreasing pH values. For chalcopyrite, the collector performances of BECTU are slightly better than those of IPETC but far superior to those of IBECTC, especially at high pH values or at low collector concentrations. The flotation performance of these collectors has been shown to be in good agreement with the amount of collector adsorbed at the mineral surface. The affinity of BECTU for the various minerals has been calculated using a multilayer adsorption model.     

Natural geobatteries associated with sulphide ore deposits,I. Theoretical studies

Any conductive sulphide ore body can generate electrical ore potentials and this can be regarded as a geobattery, with an upper positive cathode and a lower negative anode. Two mechanisms which can occur simultaneously and which appear to explain these potentials are the oxygen concentration cell (OCC) and the sulphide galvanic cell (SGC). When there is a difference of O₂ concentration between the cathode and anode, the OCC operates by contributing oxygen to the anode, and ceases when the difference is diminished. However, gradients of pH, temperature or pressure can keep the cell operating. In the SGC the sulphides dissolve at the anode (producing metal ions, sulphur and electrons), while at the cathode, either sulphides dissolve producing metal and sulphur ions, or reaction is as in the OCC. The ore potential measured in the field is the sum of the oxygen concentration cell and at times locally dominant sulphide galvanic cells.     

Natural geobatteries associated with sulphide ore deposits, II. Field studies at the viburnum trend, southeast Missouri, U.S.A.

Any conductive sulphide ore body can generate electrical ore potentials and this can be regarded as a geobattery, with an upper positive cathode and a lower negative anode. Two mechanisms which can occur simultaneously and which appear to explain these potentials are the oxygen concentration cell (OCC) and the sulphide galvanic cell (SGC). When there is a difference of O₂ concentration between the cathode and anode, the OCC operates by contributing oxygen to the anode, and ceases when the difference is diminished. However, gradients of pH, temperature or pressure can keep the cell operating. In the SGC the sulphides dissolve at the anode (producing metal ions, sulphur and electrons), while at the cathode, either sulphides dissolve producing metal and sulphur ions, or reaction is as in the OCC. The ore potential measured in the field is the sum of the oxygen concentration cell and at times locally dominant sulphide galvanic cells.     

Exploiting the dual functions of polymer depressants in fine particle flotation

Fine hydrophilic particles are known to be entrained with water in flotation of many ores. Flocculation of the hydrophilic particles by polymer depressants could potentially reduce the mechanical entrainment of these particles. This paper reports testwork completed on fine particles of several solids, iron oxide, hydroxyapatite and sphalerite, as well as on a relatively coarse quartz sample (− 75 + 38 μm). Dodecylamine was used as a collector for quartz, and several dispersants and polymer depressants, including sodium silicate, sodium metaphosphate, zinc sulfate, cornstarch, corn dextrin and carboxymethyl celluloses (with molecular weights of both 700,000 and 80,000) were used as flotation modifiers. The major part of the testwork involved flotation tests in a 200 mL flotation column. It was observed that flocculation of the fine hydrophilic particles significantly reduced their mechanical entrainment, while dispersion severely aggravated it. Thus, in the flotation separation of synthetic mixtures of the − 75 + 38 μm quartz and fine (reagent grade) iron oxide or hydroxyapatite, polymer depressants that caused flocculation performed better than those that did not cause flocculation.     

Magnesia mixture as a regulator in the separation of pyrite from chalcopyrite and arsenopyrite

The aim of this paper is to find an effective method for the separation of the undesirable constituents, namely, chalcopyrite and arsenopyrite from pyrite used for the production of H₂SO₄. A new effective method is developed for co-depressing chalcopyrite with arsenopyrite by AsI₃, followed by the addition of magnesia mixture. This method has been shown to be based on the fact that iron sites exist in the three minerals, whereas copper and arsenic sites exist only in chalcopyrite and arsenopyrite, respectively. This is coupled with the ability of both Cu(I) and Cu(II) to precipitate As(III) in the form of insoluble copper arsenides, namely Cu₃As, Cu₃As₂. In contrast, neither Fe(II) nor Fe(III) form stable arsenides. Consequently, As³⁺ ions are selectively adsorbed onto the surface of chalcopyrite. The facility for oxidizability of As(III) is well known and hence it adsorbs oxygen from the pulp and changes to As(V) of higher valency and smaller size, with ionic potential over 10. Accordingly, it yields a stable complex anion with covalent bonding, namely, [AsO₄]^3?. These newly created arsenate sites on the surface of chalcopyrite, as well as the corresponding original arsenate sites on the surface of arsenopyrite combine with magnesia mixture to form cations leading to the formation of tightly abutting strongly hydrophilic layers of … AsO₄NH₄Mg.6H₂O. The spread of this hydrophilic film on arsenopyrite and chalcopyrite surfaces leads to the screening of their surfaces, making them difficult of access for the collector, ethyl xanthate. Since the pK_a of xanthic acid occurs at pH below 3, xanthate species predominate at pH above 8 and are adsorbed selectively on the pyrite surface in sufficient quantity for its selective flotation and hence for its separation to take place in the pH range 8–9.     

焦家金矿选厂旋流器溢流产品工艺矿物学分析

焦家金矿选矿厂目前的日处理量达12000吨/天,金回收率92%。选矿厂已将破碎段产品用双螺旋分级机洗矿,洗矿的矿泥产率为7%,矿泥单独浮选,整体工艺初步实现了泥砂分选。为进一步提高选金回收率,流程改造拟将磨矿-浮选系统的旋流器溢流产品二次分级,分级的次生矿泥与洗矿矿泥进入矿泥浮选系统一并浮选,为了掌握旋流器溢流产品的性质,本文采用偏光反光两用显微镜、扫描电镜、X射线衍射仪、红外光谱和差热分析等手段进行研究。研究结果表明矿物种类主要是金属硫化物和脉石矿物,金属硫化物约占4%,脉石约占96%,金属硫化物主要是黄铁矿(70.17%)和黄铜矿(16.27%),脉石主要是石英(47.12%)和长石(15.90%)。黄铁矿和石英是重要的载金矿物,黄铁矿含金65%,石英含金20%。颗粒越细,单体颗粒含量越高,连生体颗粒含量越少;颗粒越细,黄铁矿含量越高,Au、Ag分布率越高,-0.037 mm粒级中黄铁矿含量达到73.58%,Au、Ag占到47.99%和56.60%,金分配率与黄铁矿含量成正相关;粗粒级中未发现金颗粒,中等粒级中次显微金约占30%,细粒级中次显微金约40%,金粒径在2~10μm范围内;金形状有三角形、棱角状、小粒状、不规则状等。红外光谱与差热曲线研究发现颗粒越细矿物成分趋于复杂。研究结论为磨矿分级产生的次生矿泥浮选调控提供了依据,对矿泥浮选的药剂制度调控、浮选流程确定等具有重要实际意义。     

Alteration and regeneration of sulfides by reaction with oxidizing hydrothermal solutions

Reactions between sulfides of heavy metals and solutions of hexavalent uranium sulfate at pH about 2, in the range of 200-360°C, led to replacement of pyrrhotite by marcasite-pyrite aggregate, development of bornite and pyrite after chalcopyrite, growth of regenerated chalcopyrite on the periphery of uranium oxides, replacement of chalcopyrite by bornite (with the accompanying complications, fig. 3), redepositions of chalcocite and native copper, and, in experiments with pyrite-galena and galena-marmatite pairs, redepositions of the minerals with the corresponding growth of pyrite. —V.P. Sokoloff.     

Interactive effects of the type of milling media and copper sulphate addition on the flotation performance of sulphide minerals from Merensky ore Part I: Pulp chemistry

It is well known that the chemical environment determines the success of the flotation process, however its characterisation and control is difficult to achieve. This paper, as two parts, Part I and Part II, evaluates the use of various measurements and their interpretation to gain an understanding of the influence of varying parameters such as the type of milling media and copper sulphate addition on the flotation performance of sulphide minerals from a platinum group mineral (PGM) bearing Merensky ore. It shows the complexity of interpretation and the importance of analysing flotation performance holistically. Part I focuses on the pulp chemistry and mineral potential measurements have been used to show the differences in the response of the various mineral electrodes to different conditions. The final flotation recoveries of the sulphide minerals in the ore followed the same trend as the decrease in mineral potential due to collector addition viz. chalcopyrite > pentlandite > pyrrhotite. Type of milling media and copper sulphate addition slightly affected the mineral electrode potential and flotation recovery of chalcopyrite. Addition of copper sulphate increased the recovery of pentlandite and particularly pyrrhotite due to activation by copper (II) ions. The copper activation mechanism was likely to be in the form of initial adsorption of copper hydroxide followed by reduction to Cu⁺ at the surface. However, the changes in flotation performance of the different minerals in the ore could not be completely described by the electrochemical changes, demonstrating the limitations of these measurements. Part II addresses the effect of froth stability as demonstrated by the variations in the mass and water recovery data resulting from the different milling conditions and addition of copper sulphate which emphasised the importance of considering the froth phase in the evaluation of flotation data.     

Efficient separation of zinc from zinc containing copper sulfide concentrate by chemical leaching

As the most abundant copper containing resource and zinc containing resource, chalcopyrite and sphalerite/marmatite commonly coexist as Cu-Zn mixed ores in deposits. However, it is difficult to completely separate sphalerite and chalcopyrite by flotation, thus resulting in the existence of zinc impurity in copper concentrate. Sphalerite/marmatite existed in copper sulfide concentrate as impurity may lead to severe damage of the smelting equipment, and cause the waste of copper and Zn resources, it will also decrease of the sale price of copper concentrates. Therefore, the deep separation of zinc from zinc bearing copper sulfide concentrate is of great significance. In this work, selective chemical leaching was developed to efficiently remove zinc from zinc containing copper sulfide concentrate. Under the optimal condition (i.e., sulfuric acid concentration exceed 100 g/L, temperature of 80 °C, pulp density of 10%, leaching time of 48 h), over 85% Zn was extracted into the leaching solution together with only about 10% Cu and Fe, according to the leaching experiment. Leaching slurry had good solid-liquid separation characteristics, and zinc can be further effectively recovered from the leaching solution. According to X-ray diffraction (XRD) and scanning electron microscope/energy dispersive spectrometer (SEM/EDS) analysis, chalcopyrite was the main mineralogical phase in the residues, which can be regarded as high quality copper concentrate for metallurgy. Accordingly, a new process for deep and efficient separation of Cu-Zn mixed ores has been proposed.     

The effect of particle shape and hydrophobicity in flotation

The effect of particle shape on the flotation process has been investigated in laboratory experiments with monosized spherical ballotini and ground ballotini. The particles were treated by partial methylation with trimethylchlorosilane to achieve varying degrees of hydrophobicity. In flotation, the process of film thinning and liquid drainage is critical in the formation of stable bubble–particle attachments and this is affected by the particle shape and surface hydrophobicity. Flotation tests with different particle sizes were conducted in a modified batch Denver cell. Predictions from a computational fluid dynamic model of the flotation cell that incorporates fundamental aspects of bubble–particle attachment were compared with data from flotation tests. Contact angles of the particles were measured using a capillary rise technique to indicate surface hydrophobicity. Ground ballotini generally has higher flotation rates than spherical ballotini; the results are consistent with effects from faster film thinning and rupture at rough surfaces and are well correlated by the sphericity index.