Impact of gypsum supersaturated solution on surface properties of silica and sphalerite minerals

In some sulphide mineral flotation operations, the process water contains high concentrations of calcium and sulphate ions that exceed the solubility limit of gypsum. It has been speculated that the gypsum supersaturated process water would lead to precipitation of gypsum which could coat on mineral surfaces by either nucleation or coagulation, resulting in reduced flotation recovery and selectivity. In this study, a laboratory prepared gypsum supersaturated solution is used to represent the gypsum supersaturated process water, the effect of gypsum supersaturated solution on the surface properties of silica and sphalerite minerals was investigated using zeta potential distribution measurements, scanning electron microscope (SEM), X-ray photon spectroscopy (XPS), Auger electron spectroscopy (AES), and quartz crystal microbalance with dissipation (QCM-D). Our results show that silica and sphalerite minerals carry identical surface charge (−10 mV of zeta potential) in the gypsum supersaturated solution at pH 10 although they are charged differently in simple electrolyte solution at the same pH. Needle shape gypsum precipitates are found in both silica and sphalerite minerals systems conditioned with gypsum supersaturated solution. The gypsum precipitates do not grow on the minerals surfaces but form in the bulk gypsum supersaturated solution. The heterocoagulation between the examined minerals and gypsum particles is insignificant in the gypsum supersaturated solution. It is the high calcium concentration in the gypsum supersaturated solution that has significant effect on the surface properties of silica and sphalerite minerals. The zeta potentials of silica and sphalerite in a 800 ppm calcium solution (similar to the calcium concentration in the gypsum supersaturated solution) are similar to those measured in the gypsum supersaturated solutions. Both silica and sphalerite minerals surfaces are indiscriminately coated with calcium. The surface coating of calcium results in the identical surfaces between silica and sphalerite minerals, and ultimately causes problems for the flotation separation of silica and sphalerite.     

Impact of gypsum supersaturated water on the uptake of copper and xanthate on sphalerite

Gypsum supersaturated process water has been shown to have an adverse effect on the flotation of sphalerite minerals. This study probes the mechanism of such effect by determining the uptake of copper and xanthate on sphalerite in gypsum supersaturated water using zeta potential distribution measurement, atomic absorption spectroscopy, UV–visible spectroscopy and quartz crystal microbalance with dissipation. Our results indicate that the supersaturation of water by gypsum retards the adsorption of copper and hence the sequence xanthate adsorption on sphalerite. The retardation of copper and xanthate adsorption on sphalerite is also observed by the addition of 800 ppm calcium. The adsorption of calcium is identified to compete with copper species for the reactive surface sites of the sphalerite, resulting in the reduction in copper and xanthate uptake and hence flotation recovery of sphalerite.     

Critical contact angle for coarse sphalerite flotation in a fluidised-bed separator vs. a mechanically agitated cell

This work investigates the critical contact angle for the flotation of coarse (850–1180 μm, 425–850 μm and 250–425 μm) sphalerite particles in an aerated fluidised-bed separator (HydroFloat) in comparison to a mechanically agitated flotation cell (Denver flotation cell). In this study, the surface chemistry (contact angles) of the sphalerite particles was controlled by varying collector (sodium isopropyl xanthate) addition rate and/or purging the slurry with either nitrogen (N₂) or oxygen (O₂) before flotation. The flotation performance varied in response to the change in contact angle in both the aerated fluidised-bed separator and the mechanically agitated cell. A critical contact angle threshold, below which flotation was not possible, was determined for each particle size fraction and flotation machine. The results indicate that the critical contact angle required to float coarse sphalerite particles in a mechanically agitated cell was higher than that in the fluidised-bed separator, and increased as the particle size increased. At the same particle size and similar contact angles, the recoveries obtained by the aerated fluidised-bed separator in most cases were significantly higher than those obtained with the mechanically agitated flotation cell.     

Determination of the concentrations of calcium and magnesium released from fluid inclusions of sphalerite and quartz

This study investigates the morphology of fluid inclusions trapped within a natural sphalerite and its closely intergrown quartz, and determines the total concentrations of calcium (Ca) and magnesium (Mg) released from the inclusions after grinding. The results indicated that numerous fluid inclusions with sizes from few microns to dozens of microns exist in the sphalerite and quartz. The inclusions contain abundant Ca and Mg. However, the concentrations of Ca and Mg in the inclusions of quartz are significantly lower than those of sphalerite. The inclusions were broken during the grinding process, releasing Ca and Mg to the solution; these released concentrations increased with the increase of grinding time. The maximum concentrations of Ca and Mg released from the fluid inclusions were 61.19 ppm and 5.23 ppm for sphalerite, and 3.28 ppm and 0.21 ppm for quartz, respectively. This study provides new understanding for the source of Ca and Mg in flotation pulp.     

Hydrothermal modification to improve the floatability of ZnS crystals

Crystalline structure and surface properties significantly affect the floatability of metal sulphides. In this study, a novel methodology to modify zinc sulphide (ZnS) crystals was proposed to improve the floatability of the crystals. Initially, ZnS crystals, synthesised from zinc hydroxide (Zn(OH)₂) and sulphur (S) under hydrothermal conditions, were used to assess the floatability. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were employed to analyse the crystalline structure and surface properties of the sulphides. Conventional flotation tests were performed to evaluate the floatability. The effects of mineraliser (KOH) concentration, precursor (Zn(OH)₂) concentration, hydrothermal temperature and holding time on the floatability of the ZnS crystals were investigated. The optimal flotation recovery of ZnS (82.53%) was obtained with a KOH concentration of 5 mol/L, a Zn(OH)₂ concentration of 10%, a holding time of 4 h and a hydrothermal temperature of 260 °C. Then, sludge containing fine and amorphous zinc compounds, which was generated during the disposal of metallurgical waste water, was employed to test the recovery of valuable metals using modified hydrothermal sulphidation. The results show that the recovery of Zn in the sludge can reach 66.3% under the optimal conditions.     

Froth flotation of sphalerite: Collector concentration,gas dispersion and particle size effects

This experimental work on sphalerite flotation investigated the effect on flotation performance of three particle size fractions, namely, coarse (d₈₀ = 100 μm), medium (d₈₀ = 39 μm) and fine (d₈₀ = 15 μm), bubble size distribution, superficial air velocity, and collector dosage. Bubble size distributions were characterized with the image analysis technique. The two-phase (liquid–gas) centrifugal pump and frother addition (MIBC, 5–30 ppm) allowed generating bubble diameters between 150 and 1050 μm, and air holdup ranging from 0.2% and 1.3%. Main results showed that each particle-size distribution required an optimal bubble-size profile, and that sphalerite recovery proceeded from mechanisms involving true flotation (when J_g = 0.04 cm/s and 1.9 × 10⁻⁴ M SIPX). However, cluster-flotation occurs at high collector dosage (when J_g = 0.04 cm/s and d₃₂ between 285 and 1030 μm), and requiring further investigation.     

Detachment of coarse composite sphalerite particles from bubbles in flotation: Influence of xanthate collector type and concentration

The force required to detach sphalerite ore particles from air bubbles has been measured in flotation concentrates, for particles in the size range of 150–300 μm and 300–600 μm with different degrees of liberation. An electro-acoustic vibrating apparatus, that produces typical force conditions experienced in a flotation cell, was used to measure particle–bubble detachment as a function of the vibrational acceleration. Sodium isopropyl xanthate (SIPX) and potassium amyl xanthate (PAX) collectors were used in flotation, at different concentrations. At a fixed frequency of 50 Hz, the maximum vibrational amplitude at which a particle detaches from bubble was used to calculate the particle detachment force. It was shown that changes in surface hydrophobicity (contact angle), due to variations in reagent conditions have significant impact on particles detaching from bubbles. On average, detachment of particles from oscillating bubble correlated well with xanthate concentration and hydrocarbon chain length of xanthate ions. Particles (300–600 μm) with high contact angle obviously required higher force to detach from bubbles than similar particles with lower contact angle. This correlated well with the flotation response at the different reagent conditions. SEM analysis of particles after detachment showed that fully liberated particles attached to bubbles more readily and also gave higher detachment force than composite particles. Moreover larger detachment forces were observed, on average, for particles with irregular shape compared to particles with rounded shape of the same size range.     

Surface characteristics and flotation behaviour of platinum and palladium tellurides

The telluride minerals, moncheite ((Pt,Pd)(Bi,Te)₂ and PtTe₂) and merenskyite ((Pd,Pt)(Bi,Te)₂ and PdTe₂), contribute between 20% and 45% of the PGMs present in the Platreef ore which is located in the northern limb of the Bushveld Complex of South Africa. There is evidence of these minerals reporting to the tailings and the present investigation was aimed at determining their flotation behaviour and to relate this to their surface characteristics.Microflotation, zeta potential determinations, ToF-SIMS analyses (time of flight-secondary ion mass spectrometry) and X-ray photoelectron spectroscopy (XPS) were used to characterise the flotation and surface behaviour of the synthesised samples. Copper activation of both moncheite and merenskyite samples reduced the flotation response compared with xanthate on its own. When xanthate is added on its own, it is adsorbed on the mineral surfaces at a higher concentration compared to the copper activated minerals.Oxidation of the PGE telluride minerals negatively affects the flotation performance of the Pt and Pd bismuth telluride samples respectively but not the Pt and Pd telluride samples. Grinding finer reduced recoveries and increasing the calcium ion concentration from 80 ppm to 500 ppm in the synthetic water did not negatively affect the flotation response of the PdTe₂ mineral.     

Characterisation of coarse composite sphalerite particles with respect to flotation

The flotation response of a typical zinc-lead (Zn/Pb) ore, with respect to coarse composite (sulphide/non-sulphide) particles is reported. The flotation tests were carried out on a selected feed particle size range (−600 + 75 μm, at P₈₀ of 390 μm) and the recovery of Zn composite particles analysed on a size by size basis. The best results were achieved with the use of 75 g/t sodium isopropyl xanthate (SIPX), obtaining a Zn recovery of 77%, with a significant improvement at the coarse end of the particle size distribution. Computerised scanning electron microscope (QEMSCAN) was used to characterise value mineral grain size and degree of liberation, as well as gangue and sphalerite association in particles reporting to both concentrate and tailings. A new characterisation function (Locking ratio, LR) was developed based on the data from the automated mineralogical analysis to characterise particles into two-phase composites with different degree of locking texture (simple and complex). The function, which is based on the mode of occurrence of sphalerite, grain size, proportion and composition of the constituent minerals in each particle, was used to study the flotation response of the particles with different degrees of locking. The results highlight the difference in recoverability of the sphalerite bearing particles with different degrees of locking, with simple locking texture giving higher recovery than complex locking texture, for the same overall liberation.     

Flocculation/flotation of hematite fines with anionic temperature-responsive polymer acting as a selective flocculant and collector

A novel approach to the recovery of valuable fines is the use of temperature-responsive polymers such as poly (N-isopropyl acrylamide) (PNIPAM). These polymers act as dual-function flocculants and collectors to form hydrophobic aggregates improving particle–bubble collision and attachment. The aim of this study is to investigate the flotation performance of anionic PNIPAM for an iron ore sample containing fines compared to sodium oleate, an industrial collector for hematite. PNIPAM conditioned at room temperature (25 °C, below the lower critical solution temperature (LCST)) and floated at 50 °C (above the LCST) was found to provide improved hematite grade and recoveries for particles above 20 μm, compared to sodium oleate. This was attributed to the increased selectivity and hydrophobicity of PNIPAM. Turbidity testing confirmed the flocculation of fines with PNIPAM, which deslimes the surface of the coarser particles. Below 20 μm, the hematite fines were almost completely recovered with PNIPAM. However, this recovery was not selective, attributed to the entrapment of gangue in the hydrophobic aggregates. Furthermore, conditioning of the polymer above the LCST resulted in significant losses in grade and selectivity, as the polymer self-aggregates hydrophobically and precipitates unselectively onto the closest surface.     

A modification in the flotation process of a calcareous–siliceous phosphorite that might improve the process economics

The amenability of a low-grade Egyptian phosphorite to flotation for separation of both calcareous and siliceous gangue minerals by just pH control was investigated. The ore, assaying 19.39% P₂O₅, 16.1% L.O.I. and 12.41% A.I. is mainly composed of francolite and hydroxy apatite minerals consolidated into three different phosphatic varieties according to texture and origin, i.e. coarse phospho-chem, sharp-edged phospho-clast and fine cementing phospho-mud. This was endorsed by microscopic investigation of thin sections. X-ray diffraction analysis of the ore sample showed that the main gangue minerals are calcite and quartz with minor dolomite and some gypsum.Anionic flotation of calcite, under pH4.5, was successfully conducted on the −0.25 + 0.074 mm phospho-chem fraction without any use of phosphate depressants. This was followed by direct flotation of phosphate after raising the pH to 9. Mechanical cleaning of the phospho-concentrate was carried out, without any addition of the collector to get rid of the entrained silica. About 3 kg/t of oleic acid was required for the whole process which was added step-wise 0.5 kg/t each except for the first step which was 1.0 kg/t to activate the flotation pulp. Phospho-concentrate assaying 30.54% P₂O₅, 8.7% L.O.I. and 5.76% A.I. with a P₂O₅ recovery of 64.34% was finally obtained without the use of expensive depressants, e.g. phosphoric acid or sodium silicate.A trial to explain the results in view of others’ findings and in terms of the ore mineralogical characteristics was shown.     

The role of calcium in xanthate adsorption onto sphalerite

This paper presents results of a laboratory study designed to look into the effect of calcium on sphalerite hydrophobization with xanthate making use of zeta potential, contact angle, microflotation and UV/vis spectrometry techniques. The experimental results show that xanthate adsorbs onto the mineral surface at neutral and slightly acid pH as reflected by contact angle, floatability (by microflotation) and xanthate adsorption (by UV/vis spectrometry) measurements. Apparently, xanthate adsorption is due to both the less negative surface charge of the mineral and to the presence of Zn²⁺ in equilibrium with the mineral, rather than Zn(OH)₂, which is the product of the mineral oxidation with dissolved oxygen at pH above 8. When calcium is present in the aqueous solution at concentrations similar to that of saturation for gypsum precipitation (e.g., about 0.017 mol/L), calcium apparently adsorbs on the sphalerite surface decreasing its negative charge (e.g., zeta potential) and promoting xanthate adsorption and hydrophobization, as reflected by contact angle and floatability measurements (ca. 30° and 33% recovery, respectively). Calcium adsorption appears to be favoured by the increase in pH, as reflected by the increased xanthate adsorption, thus suggesting that the calcium hydroxo-complex (CaOH⁺) is the adsorbing species. At pH 10 and 11, precipitation of calcium hydroxide (observed by SEM-EDS measurements at pH 11) appears to counteract xanthate adsorption, substantially decreasing mineral hydrophobicity. Calcium and xanthate appear to display some type of chemical interaction while calcium and dithiophosphinate do not.     

Optimization of operating parameters for coarse sphalerite flotation in the HydroFloat fluidised-bed separator

Increasing the upper size limit of coarse particle flotation has been a long-standing challenge in the minerals processing industry. The HydroFloat separator, an air-assisted fluidised-bed separator, has been used in this study to float 250–1180 μm sphalerite particles in batch flotation tests and compared to results achieved utilizing a laboratory-scale conventional Denver cell. The quiescent environment within the HydroFloat cell significantly reduces the turbulent energy dissipation within the collection zone, hence decreasing the detachment of particles from bubbles during flotation. Three operating parameters including bed-level, superficial water and gas rates have been studied, and their effect on the flotation of coarse sphalerite particles is reported. It is shown that coarse sphalerite recovery increases with increasing bed-level, superficial water and gas flow rates. However, there are thresholds for each operating parameter above which recovery starts to decrease. A comparison of recovery with a conventional Denver flotation cell indicates that the HydroFloat separator vastly outperforms the conventional flotation machine for the very coarse particles (+425 μm), and this is mainly attributable to the absence of turbulence and the minimization of a froth zone, both of which are detrimental to coarse particle flotation.     

Selective flotation of cassiterite with benzohydroxamic acid

The flotation of cassiterite mineral from gangue with a collector benzohydroxamic acid (BHA), and the interactions between the BHA and cassiterite have been investigated. It is shown through microflotation that the BHA is able to flot cassiterite very well, calcite quite limitedly, and quartz not at all, so the selective separation of cassiterite–quartz mixture was readily achieved; while for the efficient separation of cassiterite–calcite mixture containing 48.94% SnO₂, sodium hexametaphosphate (SHMP) was needed as a depressant for the gangue, and under the condition of the BHA 100 mg L⁻¹, SHMP 3.5 mg L⁻¹, a cassiterite concentrate with the grade of 85.50% SnO₂ was obtained with the recovery of SnO₂ 95.5%. Batch flotation further demonstrated that for an industrial tin slime, which contained 0.42% Sn, 13.65% SiO₂, 24.14% CaO, 16.60% MgO, 4.50% Al₂O₃ and 6.58% Fe, the tin recovery of 84.5% after one separation was reached with the concentrate grade of 1.84% Sn under the condition of the BHA 178 mg L⁻¹, SHMP 27 mg L⁻¹. In terms of zeta potential and infrared spectra studies the main interactions between the collector BHA and the mineral cassiterite in a flotation system are chemisorption with the formation of Sn–BHA compounds rather than electrostatic attractions between them.     

Bubble size measurement in electroflotation

A feature of electroflotation is the ability to create very fine bubbles, which are known to improve flotation performance of fine particles. This study was aimed at determining the hydrogen bubble size generated as a function of current density and electrode geometry. Experiments were performed in a viewing cell that allowed direct visualization of hydrogen bubbles being generated and transported away from platinum wire electrodes of 90, 120 and 190 μm in diameter. The detached bubble diameters varied between 15 and 23 μm in diameter, and for each wire diameter, were little influenced by the applied current in the range 150–350 A/m². The measurements were consistent with those predicted from a simple force balance analysis based on a H₂–Pt–0.2M Na₂SO₄ contact angle of 0.18°. Interestingly, upon detachment, the bubble size increased rapidly, recording up to an 8-fold increase in volume in the first few millimeters of rise, before approaching the steady state diameter of between 30 and 50 μm in the bulk. This increase in bubble size was found to be mostly due to the transfer of dissolve hydrogen into growing bubble while moving through the electrolyte super saturated by dissolved hydrogen gas. The equilibrium bulk diameter was found to be a function of the rate of hydrogen production, bubble nucleation rate, and dissolved gas concentration field. Consequently, electroflotation cells need to be designed to optimise the contact between the supersaturated liquid and the rising bubble plume. By doing this, the volumetric flux of bubbles will be maximised leading to improved flotation performance.     

Separation of amine-insoluble species by flotation with nano and microbubbles

Amines (alkylamines–ether amines) are employed on a large scale to separate iron ores by reverse flotation of the gangue particles (mostly quartz and silicates). Quartz gangue particles coated with amine collector are dumped in tailings dams as concentrated pulps. Then, the fraction of the amines that detach from the surfaces and the portion that is soluble in water, contaminate surface and ground-water supplies. This work presents a novel flotation technique to remove decyl-trimethyl-ether-amine (collector employed in Brazilian iron mines) from water. This amine forms precipitates at pH > 10.5 which are removed by flotation with microbubbles (MBs: 30–100 μm) and nanobubbles (NBs: 150–800 nm). Bubbles were generated simultaneously by depressurization of air-saturated water (P_sat of 66.1 psi during 25 min) forced through a flow constrictor (needle valve). The flotation by these bubbles is known as DAF-dissolved air flotation, one of the most efficient separation technologies in water and wastewater treatment. Herein, best results (80% amine removal) were obtained only after selective separation of the MBs from the NBs exploring the fact that while the NBs remain dispersed in water, the MBs rise leaving the system. The MBs, because of their buoyancy, rise too rapidly and do not collide and adhere appropriately at the amine colloids/water interface, even causing some precipitates breakage. It was found that the “isolated” NBs attach onto the amine precipitates; aggregate (flocculate) them and entrain inside the flocs before rising by flotation. Because of the low residual amine concentration in water (6 mg L⁻¹), it is believed that this flotation technique have potential in this particular treatment of residual amine-bearing effluents.     

Ferric sulphate/chloride leaching of zinc and minor elements from a sphalerite concentrate

Atmospheric leaching of a sphalerite concentrate in sulphate and chloride media was performed and the effect of several variables, such as solid/liquid ratio and oxidant (Fe(III)) concentration were investigated. The behaviour of minor elements, such as Cu, In, As, Sb, Bi, Sn and Pb, was also studied under different conditions. The results showed that using a solid/liquid ratio of 5% (w/v) it was possible to leach 95% of zinc after 2 h, with a solution of 0.5 M H₂SO₄ and Fe₂(SO₄)₃ at 80 °C. The minor elements As, Sb and Bi were also completely leached whereas copper leaching was favoured by the use of chloride medium. The oxidation of Fe(II) during the leaching tests was studied and an improvement of 20% zinc extraction was observed in an oxygenated system. Cross-current leach tests using two/three stages and a solid/liquid ratio of 10% (w/v) were performed to achieve 90% of zinc extraction. The electron microprobe analysis of the leaching residues showed no change on the sphalerite composition after the leaching, which indicates that the leaching of sphalerite involves the break down of the sulphide structure.     

On the nanobubbles interfacial properties and future applications in flotation

Nanobubbles, generations forms, basic studies and applications constitute a growing research area, included their usage in advanced mineral flotation. Yet, there are investigation needs for sustainable generation procedures, stability and understanding the nanobubbles interfacial properties and structures. Results proved that a reduction in pressure makes the super-saturated liquid suffers cavitation and nanobubbles were generated. Medium pH and solutions tested were adjusted, in the air saturation vessel, before the nanobubbles were formed, and this allowed to control (in situ) the surface charge/zeta potential-size of the forming nanobubbles. Measurements obtained with a ZetaSizer Nano equipment showed zeta potential values, in the presence of 10⁻² mol L⁻¹ NaCl, displaying sigmoidal pH behaviour between pH 2 (+26 mV) and 8.5 (−28 mV); an isoelectric point was attained at pH 4.5 and were positively charged (up to 23 mV) in acidic medium, a phenomenon which has not been previously observed. In alkaline medium, bubbles were highly negative zeta potential (−59 mV) at pH 10. The double layers appear to play a role in the formation of stable nanobubbles providing a repulsive force, which prevents inter-bubble aggregation and coalescence. Accordingly, the sizes of the nanobubbles depended on their charge and increased with pH, reaching a maximum (720 nm) around the isoelectric point (±5 mV). Highly charged and small nanobubbles (approximately 150–180 nm) were obtained in the presence of surfactants (10⁻⁴ mol L⁻¹ of alkyl methyl ether monoamine or sodium dodecyl sulphate); the zeta potential values in these experiments followed a similar trend of other reported values, validating the technique used with the nanobubbles sizes varying with pH from 150 to 400 nm. Thus, charged and uncharged stable nanobubbles can be tailor-made with or without surfactants and it is expected that their use will broaden options in mineral flotation especially if collectors coated nanobubbles (“bubble-collectors”) were employed. A detailed and updated review on factors involving stability, longevity and coalescence of nanobubbles was made. It is believed that future trend will be on sustainable formation and application of nanobubbles at industrial scale contributing to widen applied research in mineral, materials processing and liquid effluent treatment by advanced flotation.     

Pyrrhotite oxidation and its influence on alkaline amine flotation

In the production of ground calcium carbonate (GCC) for the paper industry, pyrrhotite dramatically reduces the GCC brightness and the removal of pyrrhotite through froth flotation is essential. The present study aims to study the effect of pyrrhotite oxidation on flotation recoveries during typical GCC flotation (i.e. alkaline pH, CaCO₃ saturation, amine collector). EDTA extraction and measurements of Eh (redox potential) showed a significant difference in pyrrhotite surface oxidation state when comparing exposure times of 40 and 60 min, the latter being significantly more oxidised. Microflotation results show that when pyrrhotite is exposed to air extending for more than 5 min at pH 8, the recoveries drop significantly. At higher pH, recoveries were generally low at all exposure times tested. Flotation recoveries showed strong correlation with zeta potential measurements. Bench scale flotation experiments on a sulphide bearing marble, confirmed that pyrrhotite oxidation significantly lower the GCC quality at low collector concentrations. By increasing the amine concentration, the flotation performance became independent of pH and exposure time.