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.     

Hydrodynamics and scale up in Rushton turbine flotation cells: Part 1 — Cell hydrodynamics

The effect of operating parameters on the hydrodynamics of three geometrically similar Rushton turbine flotation cells with volumes of 2.25, 10 and 50 dm³ was determined. The operating parameters investigated were superficial gas velocity (J_g), impeller rotational speed (N), and frother (methyl isobutyl carbinol, MIBC) concentration.     

Flotation of galena. Influence of grain size,of pulp deoxygenation,and of cleaning with ammonium acetate

The flotation of < 10, 10–20, and 20–40 μm galena fractions was studied. For uncleaned galena a given collector coverage produced better floatability with increasing grain size. Nitrogen had a detrimental effect only for the < 10 μm fraction, producing at a given collector coverage a recovery smaller than that obtained with air.Galena cleaned with 400 g/l ammonium acetate had very poor floatability, although xanthate abstraction was fairly high; this confirms that strong xanthate adsorption is necessary for flotation. Formation of monothiocarbonate was small in all cases, which points to a very minor influence, if any, of this compound in the flotation process.In blank flotation tests, or for very low residual xanthate concentrations, a peak at 208 nm and a shoulder at 255 nm were observed. The former was assigned to the uncomplexed Pb²⁺ ion, and the latter was tentatively attributed to the PbOH⁺ ion.Lead in solution results from dissolution of the oxidation products of galena, as galena itself has an exceedingly low solubility. The curve for total lead in solution vs. initial xanthate concentration, had a minimum for an initial xanthate concentration of 10^?5M, the further increase in dissolved lead is attributed to formation of complexes such as PbX⁺ (X = xanthate). Dissolved lead concentrations were nearly as high for cleaned as for uncleaned galena, which indicates a high oxidation rate of the mineral.     

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.     

Modified column flotation of adsorbing iron hydroxide colloidal precipitates

A promising technique for the removal of heavy metal ions from wastewater streams involved firstly the ions adsorption on a colloidal precipitate (carrier) and then the separation of the loaded flocs (coagula) by a modified column flotation. Here, the effluent feed and the carrier (ferric hydroxide) enter smoothly by the top of the column through a special diffuser, in counter current with rising bubbles (100–600 μm diameter) generated by using recycled water, surfactant and air suction through a venturi. High separation values of the column flotation of the carrier precipitates were achieved, despite the high superficial flow rate and the high Fe^+ 3 concentration utilized (> 60 mg L^− 1 Fe). No rupture of colloidal carrier aggregates was observed and a low split was ensured by monitoring the concentrate (floated product) flow rate. Results indicated that best separation was attained by controlling the medium pH (for best heavy metal ion adsorption onto the carrier), followed by sodium oleate, used as “collector” and optimizing operating parameters (conditioning, flow rates, etc.). The column throughput reached 43 m h^− 1 (m³ m^− 2 h^− 1), which is about 4 times the normal capacity of DAF-dissolved air flotation unit, the most used floater in wastewater treatment. Various metals (Cu, Ni, Pb, etc.) and molybdate ions present in synthetic and real effluent were successfully removed based on this colloidal adsorbing flotation principle. The process was also applied in a pilot scale to treat an industrial electroplating wastewater. Most of toxic metals (Cu, Ni and Zn) were reduced from initial concentrations of about of 2 to 10 mg L^− 1, to below 0.5 to 1.0 mg L^− 1, meeting local municipal discharge limits (but Cd ions). It is believed that flotation separation using medium-sized bubbles has great potential as a clean water and wastewater treatment technology.     

粉石英与红柱石的浮选分离机理研究

本文以油酸钠作为捕收剂,研究了磷酸氢二钠、柠檬酸和硅酸钠等抑制剂对粉石英与红柱石浮选分离效果的影响.结果表明,磷酸氢二钠是红柱石与粉石英浮选分离的一种优良的抑制剂;在其最佳浓度0.47×10-2 mol /L,浮选液pH值为8.5时,粉石英与红柱石浮选回收率差高达47.86％.红外光谱及Zeta电位分析结果表明,油酸钠对红柱石兼有物理和化学吸附作用,对粉石英仅有物理吸附作用,因而对红柱石有更强的捕收能力;磷酸氢二钠对粉石英表面起解吸作用,能有效抑制粉石英起浮,从而实现粉石英与红柱石的分离.     

Effects of an ultrasonic field on the flotation selectivity of barite from a barite-fluorite-quartz ore

The influence of an ultrasonic field frequency of 22 kHz and intensity of 0.5 W/cm² has been examined on the flotation of barite, fluorite and quartz as well as on their ability to adsorb dodecyl- and cetylsulphates. The tests affected the flotation of pure minerals in a Hallimond tube as well as the flotation of a natural barite-fluorite ore. It has been found that ultrasonic pretreatment of minerals causes an increase in the flotation rate of barite and a decrease in the flotation rate of fluorite. Ultrasonic pretreatment of the natural barite-fluorite ore before its flotation is the most advantageous. In this case it is possible to obtain concentrates of barite composed of a low amount of CaF₂. This may be explained by the different effects of ultrasonic vibrations on barite and fluorite which cause some improvement of the selectivity of their flotation separation.For a full explanation of these results the effects of ultrasonic pretreatment of the minerals on their adsorption properties and surface topography have been investigated, as well as the direct influence of ultrasound on the adsorption process.     

The ethylxanthate adsorption on copper-activated sphalerite under flotation-related conditions in alkaline media

Floatability and surface characteristics of sphalerite in the presence of different concentrations of copper sulphate and K-ethylxanthate, for various times of activation and collection, were studied. The resulting changes on the sphalerite surface were determined by infrated attenuated total reflection spectroscopy and correlated with electrokinetic measurement and floatability test results.The collectorless flotation of the examined sphalerite was very weak in alkaline media, independent of whether the mineral was activated with copper or without copper treatment. However, copper showed an activating effect on KEX sphalerite flotation in the alkaline region. Copper ions of high concentration provoked an “apparently depressing effect” on KEX sphalerite flotation, reacting with EX⁻ to form copper-ethylxanthate-like species in the bulk of the solution. After decantation of the solution, before KEX was added, the depressing effect disappeared and sphalerite flotation was virtually complete.Cu(I)-ethylxanthate was the main surface product under the different experimental conditions. The kinetics of the copper-ion adsorption and KEX adsorption was relatively fast.     

Precipitate flotation of copper as the sulfide,using recyclable amphoteric surfactants

An experimental study was made to identify surfactants which are effective for removal of copper from dilute aqueous solution (100–500 ppm) by precipitate flotation as the sulfide, and which at the same time can be recovered from the CuS product for recycle. Batch flotation experiments confirmed that a cationic surfactant was necessary for flotation of CuS from such dilute suspensions; however, no satisfactory way could be found for recovering cationic surfactants from the CuS. This led to consideration of amphoteric surfactants, which are cationic at low pH and anionic at high pH. It was found that a change to negative, rather than simply neutral, charge was required for efficient surfactant recovery. It was further found, through the assistance of experiments in which the CuS suspension was agitated with solvents, that certain functional groups which interact chemically with the CuS surface should also be absent from the surfactant molecule. Following this logic, Amphoterge K-2 (Lonza Chemical Co.) was identified as a suitable surfactant, provided CuS was precipitated with S^2? in excess. Tests established that 95% of adsorbed Amphoterge K-2 could be recovered by raising the pH to 11 and boiling the suspension for one hour, followed by decanting. Surfactant thus recovered was effective in a second flotation test. Foamate solids settled rapidly; such behavior would help reduce the consumption of chemicals for the pH change.Column flotation studies were made using Amphoterge K-2 for removal of Cu²⁺ present at 100 ppm and pH = 2. High removals of CuS could be obtained at concentrations of surfactant above about 25 ppm, for which conditions a substantial fraction of the surfactant remains in solution rather than being adsorbed onto the CuS. The recovery of CuS would be improved by introducing the surfactant in a separate feed, below the feed of CuS suspension. Adding some surfactant in the CuS feed, as well as in a lower feed, gave an even better recovery of CuS (99.8%) at sufficiently high surfactant loadings.     

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.     

Flotation of germanium n and p with potassium ethyl xanthate

Steady-state potential of the germanium electrode, flotation tests and results of spectrophotometric ATR (Attenuated Total Reflection) measurements of germanium surface in the presence and absence of potassium ethyl xanthate are presented.On the basis of the steady-state potentials of the germanium electrode in ethyl xanthate solutions, the standard potential E⁰ of the reaction: Ge + 2EtX^? = Ge (EtX)₂ + 2e is estimated. The pH ranges of the dixanthogen (EtX)₂ and the germanium xanthate Ge(EtX)₂ species predominance in the bulk solution are calculated. It has been established that flotation of germanium is greater than the natural floatability (in the absence of collectors) in the pH ranges where (EtX)₂ or Ge (EtX)₂ are present in the bulk solution. Spectrophotometric results reveal the presence of (EtX)₂ and Ge (EtX)₂ on the surface in the same pH ranges as is calculated for the bulk reactions.No significant differences in the surface properties and the flotation behaviour between germanium n and p have been found.     

Adsorption of barium ions by β-manganese dioxide and its activation in oleate flotation

The Ba²⁺ ion adsorption isotherms on β-MnO₂ were of the Langmuir type. The endothermic heat of adsorption (40 kJ mol^?1) is ascribed to entropy contributions associated with the $\text{Na}{}^{\mathrm{+}}\text{Ba}{}^{\mathrm{2+}}$ ion-exchange mechanism. The Ba²⁺ ion adsorption density was higher at pH 10 than that at pH 7, due to the more negative surface charge at the higher pH. Ba²⁺ ions were found to reverse the sign of the ζ potential of the MnO₂ particles.More oleate was adsorbed by β-MnO₂ in the presence of Ba²⁺ ions than in their absence. The oleate adsorption isotherms on Ba²⁺-activated MnO₂ were of the Freundlich type and indicated an exothermic process. Hallimond flotation recovery of Ba²⁺-activated MnO₂ was higher at pH 10 than at pH 7, although less oleate was adsorbed at the higher pH. At pH 7, Mn²⁺-activation led to higher recoveries than Ba²⁺-activation. It seems that the attraction between the surface and the activator plays an important rôle in determining the flotation recovery.     

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.     

Flotation behaviour of huntite (Mg3Ca(CO3)4) with anionic collectors

In this study, flotation behaviour and electrokinetic properties of huntite were determined in the presence of anionic collectors such as potassium oleate, and Flotinor FS-2. The effects of common ions that are expected in flotation pulps such as Mg²⁺ and Ca²⁺ were studied. The influences of pH and modifying reagents like sodium silicate (Na₂SiO₃·5H₂O) and carboxymethyl cellulose (CMC) on surface properties of huntite were also examined. Electrokinetic measurements showed that isoelectric point (i.e.p.) of huntite was around 8.0. Surface charge of huntite becomes positive in the presence of 10⁻² M of MgCl₂ and CaCl₂ at all pH values. According to micro-flotation test results, potassium oleate is more efficient compared with Flotinor FS-2. Mg²⁺ and Ca²⁺ ions have detrimental effect on the floatability of huntite. Na₂SiO₃ was seen to have no significant effect on the floatability of huntite. Flotation experiments with CMC indicated that it acts as a depressant on huntite.     

Treatment of Acid Mine Drainage (AMD) in South Brazil: Comparative active processes and water reuse

This work describes AMD techniques of neutralization, with lime, flocculation of the precipitates and comparative flocs/liquid separation by flotation with microbubbles or by lamellar settling (LS). The AMD treated water was characterized by its quality for recycling in terms of inorganic or organic elements, suspended or dissolved solids, among others. Two types of flocs were formed, “aerated” or not, in a special flocculation reactor, patented by this research group (RGF^®). Aerated flocs formed (within seconds) entered into contact with microbubbles under high shearing and raised-up at rates > 120 mh^− 1 allowing a rapid solid–liquid separation by flotation (HR-high rate), at about 13–15 m³m^− 2 h^− 1 loading capacity. Conversely, the non-aerated flocs settled at about 5–6 m h^− 1 in a lamella settler. Both AMD treatment techniques showed similar efficiencies (removal of ions > 90%) but the separation by lamella settling presented advantages, namely less reagents (no flotation collector required), lower power requirements and easier to operate. The operating costs (approximate values) of the AMD treatment by LS at pH 9 reaches about 0.3 US$ m^− 3 against 0.6 US$ m^− 3 for the HR-flotation process. Results found were proved to be similar to those found in recent ADM treatment installations in South Brazil. The quality of the treated water is fairly good, nearly free of heavy metals ion, low BOD (biological oxygen demand) and TOC (total organic content), low solids content and may be readily reused for irrigation, industrial processes and as wash water (among others, streets, vehicles, dust control). However, there is a need to extend the use of this treated water resource, but this, at least in Brazil, has not been legislated properly. It is concluded that this research will contribute in the discussion of this old and complex problem in acid mining effluents worldwide.     

Effects of pretreatment and aging on chromite flotation

Anionic and cationic flotation of a Stillwater Complex chromite was studied as a function of pH and various pretreatments of the mineral. Aging the ground mineral in air markedly decreased anionic (sodium dodecylsulfate) flotation below pH3 and enhanced it above pH 4–5. Such aging increased cationic (dodecylammonium chloride) flotation in the basic pH region. Mildly preheating the mineral enhanced anionic flotation. Increased conditioning time in collector solution decreased anionic flotation. Strongly acid pretreating the mineral caused it to behave like a simple charged oxide toward both anionic and cationic flotation. These phenomena appear to be related to the effect of aging on the amounts of Fe(II) and Fe(III), of Cr(III) and Cr(VI) and of Mg(II) on the mineral's surface.     

Modelling transport phenomena in a flotation de-inking column: Focus on gas flow,pulp and froth retention time

A laboratory flotation column using Venturi aerators and a vacuum system to remove froth was used to investigate the contribution of gas flow, pulp flow, cell volume and froth retention time on the ink removal efficiency and on cellulose fibres and mineral fillers loss. The increase in the gas flow from 4 to 8 L/min gave a general rise of particle transport from the pulp slurry to the froth with an ensuing strong increase in ink removal, from 75% to 85%, and water and total loss, from 10% to 40% and 15% to 30%, respectively. Whereas, the increase of the cell volume from 14 to 24 L improved ink removal from 72% to 80% without considerably affecting flotation loss. The rise of the froth retention time in the flotation cell from 5 to 20 s before removal gave a general decrease in the flotation loss from 20% to 11% without a corresponding decrease in ink removal. This trend was interpreted as reflecting poor ink drainage through the froth. The increase of both pulp and froth retention time in the flotation cell appeared as the most favourable way to improve ink flotation selectivity. A mathematical model, describing particle removal during flotation in terms of true flotation, entrainment and drainage, was proposed and used to fit experimental data.     

Oxidation-Reduction effects in the flotation of chalcocite and cuprite

A laboratory study of the batch flotation of chalcocite from chalcocite-quartz mixtures and of cuprite from cuprite-quartz mixtures with potassium ethyl xanthate as collector has shown that the oxidation-reduction state of the flotation pulp can have a pronounced influence on mineral floatabilities. At pH 11 chalcocite floated over a relatively narrow Eh range of about 300 mV; pH had no influence on the potential of the lower flotation boundary in reducing conditions but had a significant effect on the potential of the upper boundary in oxidizing conditions. Below this upper limit, the floatability was reversible with respect to Eh. Provided the Eh was in correct region chalcocite could be floated in the absence of measurable concentrations of dissolved oxygen.Cuprite displayed a high level of floatability with ethyl xanthate for which, by contrast with chalcocite, no flotation limit in reducing conditions was found; over a small range of potentials close to zero, its behaviour was strongly pH dependent.An attempt to account for the floatabilities of chalcocite and cuprite in terms of the formation of cuprous ethyl xanthate on their surfaces did not lead to correlations with the observed behaviour in reducing conditions but provided a rough correlation with the upper flotation potential limit. It is believed that more detailed and properly controlled comparative flotation studies of the chalcocite-xanthate and cuprite-xanthate systems could help to resolve some of the uncertainties associated with the effects of Eh, pH and oxygen concentration in sulphide mineral flotation.     

Efficient flotation recovery of lead and zinc from refractory lead-zinc ores under low alkaline conditions

In this study, a new flotation approach, a low-alkaline and non-desliming process, was introduced for improving lead and zinc recoveries, lowering production cost and reducing environmental pollution. Lab-scale experiments results show that the new process contributed to the flotation of the complex mixed sulfide-oxide lead and zinc ore regarding two aspects: (1) High alkaline process (pH = 12±) was replaced by low alkaline process (pH = 9±) by using collector WS (a mixture of ethyl thiocarbamate, ammonium dibutyldithiophosphate and dithiophosphate-25) and combined depressant Na₂S/ZnSO₄/Na₂SO₃ for lead sulfide flotation; (2) Non-desliming process was successfully achieved by using collector MA (a mixture of ether amine, hydroxyethyl cellulose and polyacrylic acid) and combined depressant SHP/SS (sodium hexametaphosphate/sodium silicate) for zinc oxide flotation. And 43.37% Pb in the Pb concentrate was recovered, the corresponding Pb grade was 52.73%, total 84.42% Zn was recovered by the flotation of zinc sulfide minerals and zinc oxide minerals. Moreover, the two aspects of the new approach were systematically verified from lab-scale to industrial-scale application. The industrial-scale flotation tests show that Pb recovery in Pb concentrate increased by 1.86% compared with that of original system during industrial-scale tests period, and the Pb recovery increased by 4.09% compared with that of original system before industrial-scale tests period, while the Zn operating recovery in zinc oxide concentrate improved by 19.52%. Moreover, the total reagent cost of the whole new process significantly declined by 3.93 yuan per ton of ore.