Effect of surface oxide/hydroxide products on the collectorless flotation of copper-activated sphalerite

The change in collectorless flotation of sphalerite with pH and Cu(II) concentration was correlated with the type and proportion of species present on the sphalerite surface. The solution and surface species were determined using a combination of analytical techniques including zeta potential measurement and X-ray photoelectron spectroscopy. An optimum copper concentration for maximum sphalerite flotation was identified, beyond which flotation decreased. This decrease in flotation coincided with the precipitation of copper hydroxide in neutral to mildly alkaline pH conditions. The hydrophobic polysulfide and hydrophilic copper hydroxide species were the main surface species influencing sphalerite flotation.     

Copper ion activation of synthetic sphalerites with various iron contents

The adsorption of copper ions on synthetic sphalerites of various iron contents was measured using a radiotracer technique. The correlation of Cu²⁺ ions adsorption with the pH of solution, the iron content of the solid and the degree of surface oxidation of synthetic sphalerite were determined. The experiments proved that oxidation of the surface of the sphalerite samples caused a decrease in Cu²⁺ ions sorption with the exception of samples of iron containing sphalerite. Acidity of the solution affected the adsorption of Cu²⁺ ions by deoxidized sphalerite surfaces, whereas the adsorption on oxidized surfaces did not depend on the pH.     

Characterisation of sphalerite and pyrite flotation samples by XPS and ToF-SIMS

The surface analytical techniques of X-ray Photoelectron Spectroscopy (XPS) and Time of Flight Secondary Ion Mass Spectroscopy (ToF-SIMS) have provided information on the type and concentration of species on the surface of sphalerite and pyrite particles in flotation concentrate and tail samples, but also on their distribution on each particle and across particles of different sizes. From this surface analytical study, a more accurate interpretation of the flotation results of sphalerite and pyrite minerals in a mixed mineral system could be made as a function of the concentrations of copper sulphate activator and xanthate collector, and particle size. In particular, it was found that sphalerite particles reporting to the concentrate are larger in size and contain less iron hydroxide on their surface than particles reporting to the tail. As for the pyrite particles, their lower recovery than the sphalerite particles is the result of a larger proportion of iron hydroxide on their surface inhibiting copper and collector adsorption.     

Depression mechanisms of sodium bisulphite in the xanthate-induced flotation of copper activated sphalerite

The effect of sodium bisulphite on the xanthate-induced flotation of copper-activated sphalerite has been studied using batch flotation testing, surface analysis techniques (XPS and ToF-SIMS), and FTIR. The various techniques have been used to identify the mechanisms of interaction of sulphite ions with both collector and the sphalerite surface. The results indicate that sodium bisulphite depressed the flotation of sphalerite particles pre-treated with copper and xanthate at pH 9 with nitrogen and air purging. It was found that sodium bisulphite interacts with the sphalerite surface, as well as with xanthate in its adsorbed state. Based on the evidence obtained in the present study, and in conjunction with previous work, the mechanisms involved in the depression of the xanthate-induced flotation of copper-activated sphalerite by sulphite are proposed. It is suggested that copper xanthate decomposition on the surface of the activated sphalerite and the decomposition of the hydrophobic copper-sulphide-like species on the sphalerite surface are the active mechanisms for sphalerite depression by sodium bisulphite.     

Isopropylxanthate ions uptake by modified natural zeolite and removal by dissolved air flotation

This work describes a laboratory study concerning the adsorption of isopropylxanthate ions onto modified zeolites particles. The separation of the loaded carrier and their removal, from aqueous solutions, was conducted by flocculation followed by dissolved air flotation, DAF. The zeolite employed was a natural sample (approximately 48% clinoptilolite and 30% mordenite) which was previously treated with sodium ions (activation) and modified with copper ions (Cu–Z) before the xanthate ions uptake. Adsorption capacities (q_m) for Cu–Z were 0.34 meq g^− 1 for the powdered form, and 1.12 meq g^− 1 for the floc form. The adsorption capacity for the floc form appears to involve an enhanced electrostatic adsorption due to the positive sites on the floc surface. In all cases, the isopropylxanthate concentration in the treated water was found to be negligible (< 0.04 mg L^{− 1}). The flotation technique showed to be a fast process, requires a low recycle ratio (20%) in air saturated water, and the treated water ended up with a very low residual turbidity (6.8 NTU). It is believed that this adsorption–flotation technique, here named adsorptive particulate flotation, using activated and modified natural zeolite has a high potential as an alternative for pollutants removal (copper and isopropylxanthate ions) from waste mining effluents.     

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.     

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.     

Bulk compositions of intimate intergrowths of chalcopyrite and sphalerite and their genetic implications

To determine the bulk chemical compositions of chalcopyrite containing starlike sphalerite and sphalerite including dotlike chalcopyrite, specimens from various types of ore deposits in Japan were used for modal and electron microprobe analyses. According to the analytical results, most of the measured zinc contents in chalcopyrite containing starlike sphalerite are less than 0.8 at%, corresponding to the maximum solubility of zinc in chalcopyrite as determined experimentally at 400°C. However, specimens from the Maruyama deposit in the Tsumo mine contain 1.2–1.4 at% Zn, which are within the solubility limit of an intermediate solid solution (ISS) above 400°C. It is therefore concluded that starlike sphalerite in chalcopyrite are exsolution products derived from primary chalcopyrite solid solution and/or zincic ISS. Measured copper contents in sphalerite including dotlike chalcopyrite yield considerably higher values, i.e., 1.5–6.0 at%, which exceed the solubility limits of copper in sphalerite solid solution as determined experimentally. This result suggests that not all the chalcopyrite dots were exsolved from sphalerite, but that most of them are the product of some other mechanisms.     

5-alkylsalicylaldoximes as collectors in flotation of sphalerite,smithsonite and dolomite in a Hallimond tube

Flotation tests for sphalerite, smithsonite and dolomite were carried out in a Hallimond tube at various pH values and two concentrations of collector.Adsorption of 5-alkylsalicylaldoximes on the surface of minerals was examined and isotherms for 5-butylsalicylaldoxime plotted.It was shown that sorption intensity of 5-alkylsalicylaldoximes on the surface of minerals decreased in the order: smithsonite, sphalerite and dolomite.Relationship between length of aliphatic chain and collecting activity of 5-alkylsalicylaldoximes was investigated in microflotation tests in a Hallimond tube.5-Propylsalicylaldoxime proved to have the best selectivity in flotation for the range of parameters studied, taking the difference in flotation rates of smithsonite and dolomite as a criterion.It was found that modifications of pH value resulted in changes in both adsorption and flotation.     

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.     

Formation and recognition of alkyl xanthyl thiosulphates in sulphide ore flotation liquors

Alkyl xanthyl thiosulphates (R.OCSS.S₂O₃^?) (RXT^?) are formed in solution by mild oxidation (e.g. by I₂) of solutions containing both xanthate and thiosulphate. They can also be formed by reaction of Cu²⁺ with xanthate and thiosulphate, reaction of dixanthogen with thiosulphate, and by reaction of xanthate with tetrathionate; these last three reactions can occur in flotation pulps in slightly acid or alkaline solutions (pH 5–10).Alkyl xanthyl thiosulphates are stable in acid and neutral solution; the solutions have a UV absorption maximum at 289 nm. In strongly alkaline solution (pH 12) RXT^? decomposes within a few minutes to yield a xanthate (mostly) plus a little perxanthate. At pH 10 this decomposition to xanthate takes about 48 h. At pH 7–9 RXT^? is relatively stable. RXT^? is not extracted from aqueous solution with common solvents (chloroform, iso-octane, cyclohexane, or ether). It forms a water-insoluble adduct with cetyltrimethyl-ammonium bromide (CTAB); this adduct can be extracted into chloroform, and the extract has a UV absorption maximum at 296 nm.RXT^? was found in solutions from the gangue-sulphide flotation section at Renison Ltd, the zinc flotation circuit and the copper flotation circuit at Mount Isa Mines Ltd, and the lead flotation section of The Zinc Corporation Ltd. The presence of RXT^? in operating flotation plants has various practical and theoretical implications.     

Effect of surface oxidation and iron contents on xanthate ions adsorption of synthetic sphalerites

Abstraction of xanthate ions from solution by copper-activated synthetic sphalerites with various iron contents was measured. It was found that raising the iron content in the samples caused a decrease in xanthate ions abstraction. For sphalerite samples characterized by the same percentage of iron deoxidized surfaces took up more xanthate ions than oxidized surfaces.Surface coverage by EtX^? ions was determined to be less than one monolayer. These values were compared with copper ion coverage at sphalerite surface. The amount of EtX^? ions abstracted from solution was noted to be independent of the pH of the solution in the range from 6 to 10 pH units, above $\text{pH}\text{=10}$ a decrease in the abstraction was observed.     

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.     

水悬浮体系中凹凸棒石与Cu2+作用机理

研究矿物吸附重金属性能和机理,对正确认识矿物吸附性质、环境矿物材料应用研究以及重金属环境化学行为具有重要理论和实际意义。凹凸棒石是重要粘土矿物之一,也是重要的环境矿物材料,其吸附净化功能潜在应用受到广泛关注。在制备凹凸棒石纯样基础上,进行了凹凸棒石吸附Cu^2 单因素实验,吸附前后溶液pH值变化观测和吸附Cu^2 后凹凸棒石表面结构高分辨透射电镜调查。结果表明,从表面来看,凹凸棒石对Cu^2 的吸附性能主要受振荡速度、吸附时间、初始溶液pH值、吸附剂用量等因素影响,但实际上,凹凸棒石对Cu^2 的吸附作用主要是凹凸棒石诱导的Cu^2 水解沉淀作用以及凹凸棒石(带负电荷)与氢氧化铜(带正电荷)正负电荷胶体颗粒的互相作用,这有别于严格意义的矿物界面吸附作用。产生这种作用的机制在于凹凸棒石属于天然纳米矿物材料,具有较高的表面化学活性,凹凸棒石一水悬浮体系中凹凸棒石表面水解呈现出碱性,结果导致吸附平衡水溶液pH值较初始水溶液有较大程度的升高,达到Cu^2 水解基本完全的pH条件.     

Hydrothermal deposition on the East Pacific rise at 21°N

In the spring of 1979, 350°C springs precipitating hydrothermal sulphides and sulphates directly on to the sea-floor were discovered on the crest of the East Pacific Rise (EPR) at 21°N by the astonished scientific party of the RISE submersible expedition. These hot springs are within a linear field of active and inactive hydrothermal vents extending 6 km along the rise axis. Typically the mineral deposits at EPR, 21°N consist of basal sulphide mounds surmounted by mineralized sulphide-sulphate edifices, or “chimneys”, reaching heights up to 13 m above the sea floor. The mounds rest directly on fresh basalt and cover areas up to 450 m². Chimneys atop mounds may be active or dead. The hottest active chimneys (350°C) spew forth fluids blackened by fine-grained sulphide precipitates, dominantly hexagonal pyrrhotite and iron-rich sphalerite. These “black smokers” are distinguished from cooler “white smoker” chimneys which are encrusted by worm tubes and emit milky fluids bearing amorphous silica, barite, and pyrite.     

The effect of dextrin on surface properties and the flotation of molybdenite

The effect of dextrin on molybdenite surface properties has been investigated experimentally through measurements of zeta potentials, adsorption densities, contact angles, Hallimond tube flotation and oil flotation response. These studies indicate that the adsorption of dextrin on molybdenite occurs through physical interaction with the surface, possibly due to hydrophobic bonding. The hydrophobic bonding mechanism is in accord with the magnitude of the adsorption free energy, which was estimated to be—5.4 kcal per mole of dextrin monomers. Dextrin was found to be a very effective depressant for the air flotation of molybdenite in the absence of a collector, whereas it does not effectively depress molybdenite in an oil flotation process using iso-octane. This has been discussed qualitatively from the contributions of electrical double layer repulsion, van der Waals' attraction, and hydration effects.     

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.     

Perxanthates — A new factor in the theory and practice of flotation

A compound with a UV absorption maximum at 348 nm was observed in Mount Isa copper flotation plant solution. This spectrum was similar to that of the product of reaction of xanthate and peroxide in dilute, alkaline aqueous solution. The compound was termed perxanthate (more correctly “O”-alkyl dithiomonoperoxycarbonate).A new compound, ammonium sec-butyl perxanthate (C₄H₉ OCSSO·NH₄), was prepared by reacting potassium sec-butyl xanthate and hydrogen peroxide in dilute alkaline solution, acidifying, extracting into iso-octane, and precipitating with anhydrous ammonia. Solutions of this compound were compared with solutions containing the Mount Isa compound. Each compound was found to have the same UV absorption spectrum in a given solvent (alkaline aqueous, acid aqueous, chloroform, iso-octane, iso-amyl alcohol, and n-butyl acetate), but the spectra were different in different solvents (especially in alkaline and acid aqueous solutions). Both compounds could be extracted from acid, but not alkaline, aqueous solutions by organic solvents, and both had similar IR and mass spectra.It was concluded that the perxanthate in plant solution resulted from reaction of xanthate with peroxide derived from reduction of oxygen during flotation. This lends credence to the electrochemical theory of flotation and has some important theoretical and practical implications.     

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.     

Stratiform copper deposits and interactions with co-existing atmospheres, hydrospheres, biospheres and lithospheres

Fundamental evidence from world-class stratiform copper deposits repeatedly indicates that they originated by a two-stage mineralization process: a syn-diagenetic enrichment of the host sediment in iron sulfide, followed by a sub-surface addition of copper during early diagenesis of the sediment. In contrast to the previously favored syngenetic hypothesis, which suggested an open equilibration between atmosphere, hydrosphere, biosphere and upper lithosphere during mineralization, the two-stage model implies that only the initial deposition of iron sulfides should take place with open exchanges between the upper “spheres”. The sub-surface emplacement of copper should occur in relative isolation from surface environments and, therefore, the occurrence and distribution of stratiform copper deposits through time and space should not be used to make direct interpretations of contemporaneous conditions in the upper “spheres”.