Studies on the flotation of sulphides. II. The effect of urea on the flotation of zinc sulphide

The effect of three hydrophilic non-electrolytes on the flotation of ZnS has been studied using a Fuerstenau microflotation cell. The rate of flotation increases with increasing concentrations of urea(OC(NH₂)₂), but is unaffected by thiourea and slightly decreased by sucrose. This effect of urea was observed with all samples of ZnS (synthetic and natural) studied, is unaffected by extensive purification of the urea and by the presence or absence of O₂, and is reversed by dilution. Urea also increases the rate of flotation (in a Partridge and Smith cell) in the absence of frother. Surface tension measurements showed the absence of detectable concentrations of surfactants in the urea. The presence of urea has no effect on the rate of sedimentation (i.e. on the degree of aggregation) of ZnS or on the volume of water carried over during flotation. It is suggested that the effect of urea is (at least in part) to increase the rate of bubble-particle attachment by modifying the structure of water.     

Studies on the flotation of sulphides. III. A manometric study of the uptake of O2 by aqueous suspensions of zinc sulphide particles

A modified Warburg manometer has been used to study the relatively slow uptake of O₂ by particles of pure synthetic ZnS in aqueous suspension at 26°C. When dry ZnS is placed in unbuffered water there is an immediate ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{< 5}\text{s}$) fall in pH (corresponding to the uptake of one HO^? for approximately every 12.5 surface atoms of zinc) and a fairly rapid ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{～ 5}\text{min}$) uptake of O₂ (corresponding to one O₂ for approximately every 20 surface atoms of zinc), followed by a slow steady-state uptake of O₂ (equivalent to one O₂ per approx. 5000 surface atoms of zinc per min). The subsequent addition of Cu(II) ions causes an immediate increase in the rate of O₂-uptake which gradually reverts to the steady-state rate; this provides evidence for a distinct intermediate stage in the formation of Cu(II)-activated ZnS.     

Electrochemical studies of sulphides,I. The electrocatalytic activity of galena,pyrite and cobalt sulphide for oxygen reduction in relation to xanthate adsorption and flotation

The electrocatalytic activity of galena, pyrite and Co₃S₄ for oxygen reduction has been studied by potentiostatic methods. Open circuit potentials of the sulphide electrodes have also been measured as a function of pH in nitrogen, air and oxygen atmospheres and also in the presence of H₂O₂ and ethyl xanthate. The adsorption of xanthate on sulphides was followed by observing bubble attachment to the electrodes.The catalytic activity for oxygen (or H₂O₂) reduction (the cathodic currents), the electrode potentials and the xanthate adsorption as shown by bubble attachment within certain pH limits, all varied as $\text{Co}{}_3\text{S}{}_4\text{> pyrite (≈ PbS in H}{}_2\text{O}{}_2\text{) ? PbS}$ indicating considerable dependence of the redox processes in flotation on the d - electron character of the sulphides.In the absence of oxygen, xanthate is probably bonded to the water structure of the surface through hydrogen-bonding, thus keeping the surface hydrophilic. Such adsorption reduces the electrode potential and inhibits oxygen reduction.     

The effect of hydrodynamic conditions on true flotation and entrainment in flotation of a complex sulphide ore

The separation efficiency and selectivity of flotation are directly proportional to recoveries of the mineral species in the feed due to true flotation and entrainment. In this study, effects of the hydrodynamic conditions on true flotation and entrainment were investigated by using a fractional factorial experimental design. A method previously described in the literature was applied to determine the contributions of true flotation and entrainment in flotation of a complex sulphide ore. In order to apply the method, the kinetic flotation tests were conducted under various hydrodynamic conditions defined by some physical variables. Some of these tests were conducted in the presence and absence of a collector to evaluate the self-induced floatability. The selectivity index of the mineral species for entrainment was seen to be suitable evaluation of the non-selectivity and efficiency of the entrainment. Furthermore, the results of the size-by-size analysis of the froth products indicated that the presence of the self-induced hydrophobic particles in the feed is as important as the presence of very fine particles for accurate estimation of true flotation and entrainment in flotation of a complex sulphide ore. In addition, the estimated results for entrainment in flotation of the complex sulphide ore can be misleading. Therefore, a new approach would be necessary to determine the contributions of true flotation and entrainment in flotation of a complex sulphide ore.     

Electrochemical studies of sulphides,II. Measurement of the galvanic currents in galena and the general mechanism of oxygen reduction and xanthate adsorption on sulphides in relation to flotation

Galvanic currents were measured by short circuiting two half cells; PbS  N₂ (g)  KNO₃ | KNO₃  O₂ (g) or H₂O₂  PbS, and then after adding xanthate to the l.h.s. cell. Such addition of xanthate resulted in a 10 fold (with O₂ in the r.h.s. cell) and 100 fold (with H₂O₂ in r.h.s. cell) increase in the short circuit and steady state currents and also lead to bubble attachment on galena in the l.h.s. cell, in nitrogen atmosphere. The results indicated a heterogeneous, two site electrochemical mechanism for the reduction of oxygen and oxidative adsorption of xanthate on galena.     

Supergene alteration of sulphides,I. A chemical model based on massive nickel sulphide deposits at Kambalda,Western Australia

An electrochemical model for the weathering of massive sulphide deposits that have undergone conditions similar to those affecting the Kambalda nickel deposits is presented. Galvanic corrosion due to aeration of the top of the ore body near the water table results in a deep anodic reaction whereby primary sulphides undergo an oxidative transition to sulphur-rich violarite—pyrite ore and also a shallow oxidative anodic reaction where the violarite—pyrite ore is oxidised to sulphate and gossanous oxides. Electrons are conducted through the ore from the anodes to the cathode where dissolved oxygen radicals are reduced and the corrosion cells are completed by ionic transport through the groundwaters to the anodic regions that can be some 200 m deep in the case of deep weathering processes. The kinetics of the weathering are described in terms of resistance to the flow of corrosion currents in the electrochemical cells. The effect on the model of physical perturbations such as rising and falling water table, faulting, etc. is discussed.     

The adsorption of gold(I) hydrosulphide complexes by iron sulphide surfaces

The adsorption of gold by pyrite, pyrrhotite, and mackinawite from solutions containing up to 40 mg/kg (8 μm) gold as hydrosulphidogold(I) complexes has been measured over the pH range from 2 to 10 at 25°C and at 0.10 m ionic strength (NaCl, NaClO₄). The pH of point of zero charge, pH_pzc, has been determined potentiometrically for all three iron sulphides and shown to be 2.4, 2.7, and 2.9 for pyrite, pyrrhotite, and mackinawite, respectively. In solutions containing hydrogen sulphide, the pH_pzc is reduced to values below 2. The surface charge for each sulphide is therefore negative over the pH range studied in the adsorption experiments. Adsorption was from 100% in acid solutions having pH < 5.5 (pyrite) and pH < 4 (mackinawite and pyrrhotite). At alkaline pH’s (e.g., pH = 9), the pyrite surface adsorbed 30% of the gold from solution, whereas the pyrrhotite and mackinawite surfaces did not adsorb.The main gold complex adsorbed is AuHS°, as may be deduced from the gold speciation in solution in combination with the surface charge. The adsorption of the negatively charged Au(HS)₂⁻ onto the negatively charged sulphide surfaces is not favoured. The X-ray photoelectron spectroscopic data revealed different surface reactions for pyrite and mackinawite surfaces. While no change in redox state of adsorbent and adsorbate was observed on pyrite, a chemisorption reaction has been determined on mackinawite leading to the reduction of the gold(I) solution complex to gold(0) and to the formation of surface polysulphides. The data indicate that the adsorption of gold complexes onto iron sulphide surfaces such as that of pyrite is an important process in the “deposition” of gold from aqueous solutions over a wide range of temperatures and pressures.     

Sulphidizing reactions in the flotation of oxidized copper minerals,II. Role of the adsorption and oxidation of sodium sulphide in the flotation of chrysocolla and malachite

The rate of consumption of sulphide in the sulphidizing reactions of malachite and chrysocolla has been measured. The oxidation of sulphide ions at the surface of sulphidized chrysocolla was shown to take place. The influence of thiosulphate anions on the xanthate flotation of sulphidized malachite and chrysocolla was investigated and it was shown to depress the flotation of chrysocolla strongly.The result suggest, that the presence of thiosulphate as a product of simultaneous oxidation can be one of the reasons for the more difficult flotation of sulphidized chrysocolla.     

Adsorption of aqueous Pb(II), Cu(II), Zn(II) ions by amorphous tin(VI) hydrogen phosphate: an excellent inorganic adsorbent

Amorphous tin(VI) hydrogen phosphate (ATHP) was synthesized using the liquid phase precipitation method and served as an adsorbent to remove Pb(II), Cu(II), and Zn(II) from aqueous solutions. The ATHP was characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption–desorption techniques. Adsorption properties were evaluated as a function of pH, reaction time, concentration of reactants, and salinity. Their equilibrium adsorption data were modeled using Freundlich, Langmuir, and Dubinin–Kaganer–Radushkevich isotherms, respectively. The results revealed that adsorption equilibrium reached within 180 min. ATHP indicated good adsorption even below the pH_ZPC, and best adsorption at pH 5 for Pb(II) and Cu(II) and at pH 5.5 for Zn(II) was observed. Equilibrium data fitted better to the Langmuir model for Pb(II) and Cu(II) and fitted better to the Freundlich model for Zn(II). The saturated adsorption capacities deduced from the Langmuir model were 2.425, 1.801, and 0.600 mmol/g for Cu(II), Pb(II), and Zn(II), respectively, indicating an adsorption affinity order of Cu > Pb > Zn. There is a negative correlation between the concentration of NaCl and adsorption capacity of ATHP, yet ATHP still exhibited excellent adsorption having an adsorption capacity of 19.35, 15.16, 6.425 mg/g when the concentration of NaCl was 0.6 mol/L. The free energy (E) was 12.33, 10.70, and 14.74 kJ/mol for Pb(II), Cu(II), and Zn(II), respectively. An adsorption mechanism based on ion exchange between heavy metal ions and H⁺ in the ATHP is proposed. Furthermore, the used ATHP was regenerated by HCl solution and the adsorbent was used repeatedly.     

Galvanic interaction between grinding media and arsenopyrite and its effect on flotation: Part II. Effect of grinding on flotation

Arsenopyrite floatability was correlated with the galvanic current, calculated from polarization curves measured during grinding, as well as the amount of oxidized iron, measured by EDTA extraction, in the mill discharge. The adverse influence of galvanic interaction during grinding on arsenopyrite floatability was quantified.     

The effect of iron on montmorillonite stability. (II) Experimental investigation

Several designs proposed for high-level nuclear waste (HLW) repositories include steel waste canisters surrounded by montmorillonite clay. This work investigates montmorillonite stability in the presence of native Fe, magnetite and aqueous solutions under hydrothermal conditions. Two series of experiments were conducted. In the first, mixtures of Na-montmorillonite, magnetite, native Fe, calcite, and NaCl solutions were reacted at 250 °C, P_sat for between 93 and 114 days. In the second series, the starting mixtures included Na-montmorillonite, native Fe and solutions of FeCl₂ which were reacted at temperatures of 80, 150, and 250 °C, P_sat, for 90-92 days. Experiments were analysed using XRD, FT-IR, TEM, ICP-AES, and ICP-MS. In the first series of experiments, native Fe oxidised to produce magnetite and the starting montmorillonite material was transformed to Fe-rich smectite only when the Fe was added predominantly as Fe metal rather than Fe oxide (magnetite). The Fe-rich smectite was initially Fe(II)-rich, which oxidised to produce an Fe(III)-rich form on exposure to air. The expansion of this material on ethylene glycol solvation was much reduced compared to the montmorillonite starting material. TEM imaging shows that partial loss of tetrahedral sheets occurred during transformation of the montmorillonite, resulting in adjacent layers becoming H-bonded with a 7 Å repeat. The reduced swelling property of the Fe-smectite product may be due predominantly to the structural disruption of smectite layers and the formation of H-bonds. Solute activities corresponded to the approximate stability field calculated for hypothetical Fe(II)-saponite. In the second series of experiments, significant smectite alteration was only observed at 250 °C and the product contained a small proportion of a 7 Å repeat structure, observable by XRD. In these experiments, solute activities coincide with berthierine. The experiments indicate that although bentonite is still a desirable choice of backfill material for HLW repositories, some loss of expandability may result if montmorillonite is altered to Fe-rich smectite at the interface between steel canisters and bentonite.     

Preparation of a novel two-dimensional carbon material and enhancing Cu(II) ions removal by phytic acid

A novel two-dimensional carbon material using phytic acid-functionalized graphene oxide was successfully synthesized by a simple hydrothermal method. Properties of the material were characterized by SEM, FT-IR, FITR-Rama and BET. Some factors like contact time, pH, and temperature were studied to investigate the adsorption characteristics on Cu(II) ions of the material. Experiment results showed that the material can reach equilibrium adsorption in 20 min and get maximum adsorption capacity (316.586 mg g) under the condition of pH 4.0, 304 K. The adsorption of Cu(II) ions was an exothermic and spontaneous process, and could be better simulated by the pseudo-second-order kinetics and Freundlich isotherm model.     

Supergene alteration of sulphides,VI. The binding of Cu,Ni, Zn,Co and Pb with gossan (iron-bearing) minerals

The results of experimentally coprecipitating the base metals Cu, Ni, Zn, Co and Pb with iron as it is oxidised and hydrolised are presented in conjunction with the data from anodically weathering 19 different sulphide ore electrodes.At pH-values above 6 the base metals are shown to be retained in the solid precipitates with Fe“Ni, Fe“Zn and Fe“Co pyroaurite-type phases forming. A 7–8-Å interlayer spacing predominates at higher pH while at the pH of 6–7 where the base metals become more soluble, a 10–11-Å spacing forms. The Fe“Cu system gives posnjakite and brochantite phases that are likely to have a high Fe content, as well as the oxides tenorite and cuprite. The base metals can be leached out of these precipitates if they are acted on by weakly acid leachants, but alkaline leaching shows retention of the base metals.Below pH 6 the base metals are more soluble, with Cu and Pb being retained to some degree in the precipitates as Fe-oxyhydroxide minerals form.In the light of experiments that show the mechanisms involved in the formation of all of these phases, two mechanisms for the formation of iron minerals during the weathering of sulphides to gossans are discussed. One at higher pH that gives rise to retention of base metals with the iron minerals, and the other giving rise to a low pH and the solubilising of the base metals.     

The concentration of Cu(II), Pb(II) and Zn(II) from aqueous solutions by particulate algal matter

Experimental studies of the reactions of Cu(II), Pb(II), and Zn(II) in aqueous solutions with organic matter derived from fresh samples of the green filamentous algae Ulothrix spp. and the green unicellular algae Chlamydomonas spp. and Chlorella vulgaris show that, under suitable conditions, a significant proportion of the metals is removed from solution by sorption onto the particulate organic matter of the algal suspension.The metal sorption is strongly suppressed by H⁺ but is only marginally influenced by the proportion of whole cells in the suspension and by complexing of metals in solution by the soluble organic matter. The presence of relatively small amounts of the cations Na⁺ and Mg²⁺ in solution reduces the sorption of Zn(II) to near zero, but Pb(II) and Cu(II) sorption occurs to an appreciable extent even in strong brines. This may be a means for the selective precipitation of Pb(II) from brines rich in Pb(II) and Zn(II).Metal “saturation” values indicate that particulate algal matter of the type used in these experiments could sorb sufficient quantities of metal to form an ore deposit if a weight of organic matter of similar order of magnitude to that of the inorganic sediments in the deposits was available. However, the metal sorption is an equilibrium reaction, and the experimentally determined “enrichment factors” suggest that the “saturation” values could be approached only in solutions whose metal contents were initially at least two orders of magnitude above those of normal seawater.     

Modeling the adsorption of Cd (II), Cu (II), Ni (II), Pb (II) and Zn (II) onto montmorillonite

The adsorption of five toxic metallic cations, Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II), onto montmorillonite was investigated as a function of pH and ionic strength and a two-site surface complexation model was used to predict the adsorption data. The results showed that in the lower pH range, 3∼6 for Cd, Cu, Ni and Zn, and 3∼4.5 for Pb, the adsorption was greatly affected by ionic strength, while in the higher pH range, the adsorption was not. In the lower pH range, the metallic cations were mainly bound through the formation of outer-sphere surface on the permanently charged basal surface sites (≡X⁻), while in the higher pH range the adsorption occurred mainly on the variably charged edge sites (≡SOH) through the formation of inner-sphere surface complexes. Acid-base surface constants and metal binding constants for the two sites were optimized using FITEQL. The adsorption affinity of the five metallic cations to the permanently charged sites of montmorillonite was Pb > Cu > Ni ≈ Zn ≈ Cd, while that to the variable charged sites was Pb ? Cu > Zn > Cd > Ni.     

Activation of zinc sulphide with CuII,CdII and PbII: I. Activation in weakly acidic media

During the activation of zinc sulphide with the heavy metal ions Cu^II, Cd^II and Pb^II, metal-ion uptake follows a logarithmic dependence on time. A reaction mechanism is proposed which is consistent with experimental observations. Incident radiation has a strong influence on the activation reaction, an effect which is interpreted in terms of semiconductor theory.     

The effect of thermal treatment on the flotation of chrysocolla

Flotation studies using a Hallimond tube have been carried out on purified samples of chrysocolla. The results confirm that by heating the sample to 550°C, flotation of the sulphidized sample with amyl xanthate is considerably improved. Flotation with sodium dodecyl sulphate is also considerably higher. The recovery with cationic collectors is not modified by the thermal treatment.Electrophoretic mobility measurements and flotation studies using benzene instead of air for the collection of the particles suggest that the increase in flotation after thermal treatment is a consequence of (1) an increase in the solubility of copper ions and their adsorption on to the surface of the particles, and (2) an increase of the intrinsic hydrophobicity of the particles due to condensation of some of the free silanol groups on their surface.