Advances in depressants for flotation separation of Cu–Fe sulfide minerals at low alkalinity:A critical review

The flotation separation of Cu–Fe sulfide minerals at low alkalinity can be achieved using selective depressants.In the flotation system of Cu–Fe sulfide minerals,depressants usually preferentially interact with the pyrite surface to render the mineral surface hydrophilic and hinder the adsorption of the collector.This review summarizes the advances in depressants for the flotation separation of Cu–Fe sulfide minerals at low alkalinity.These advances include use of inorganic depressants (oxidants and sulfur–oxygen compounds),natural polysaccharides (starch,dextrin,konjac glucomannan,and galactomannan),modified polymers (carboxymethyl cellulose,polyacrylamide,lignosulfonate,and tricarboxylate sodium starch),organic acids (polyglutamic acid,sodium humate,tannic acid,pyrogallic acid,salicylic acid,and lactic acid),sodium dimethyl dithiocarbamate,and diethylenetriamine.The potential application of specific inorganic and organic depressants in the flotation separation of Cu–Fe sulfide minerals at low alkalinity is reviewed.The advances in the use of organic depressants with respect to the flotation separation of Cu–Fe sulfide minerals are comprehensively detailed.Additionally,the depression performances and mechanisms of different types of organic depressants on mineral surfaces are summarized.Finally,several perspectives on depressants vis-à-vis flotation separation of Cu–Fe sulfide minerals at low alkalinity are proposed.

Comparative studies on flotation of aluminosilicate minerals with Gemini cationic surfactants BDDA and EDDA

Gemini quaternary ammonium salt surfactants, butane-a, co-bis（dimethyl dodeculammonium bromide） （BDDA） ethane-a, fl-bis（dimethyl dodeculammonium bromide） （EDDA） were adopted to comparatively study the flotation behaviors of kaolinite, pyrophyllite and illite. It was found that three silicate minerals all exhibited good floatability with Gemini cationic surfactants as collectors over a wide pH range, while BDDA showed a stronger collecting power than EDDA. FTIR spectra and zeta potential analysis indicated that the mechanism of adsorption of Gemini collector molecules on three silicate minerals surfaces was almost identical for the electronic attraction and hydrogen bonds effect. The theoretically obtained results of density functional theory （DFT） at B3LYP/6-31G （d） level demonstrated the stronger collecting power of BDDA presented in the floatation test and zeta potential measurement.

Recent advances in electrochemistry of sulfide mineral flotation

The electrochemical basis for understanding the interaction of thiol collectors with sulfide minerals is reviewed. Spectroscopic techniques are being increasingly applied to augment electrochemical studies and provide unequivocal identification of species formed at mineral surfaces in flotation systems. These include X ray photoelectron, Fourier transform infrared spectroscopy and, more recently, surface enhanced Raman scattering spectroscopy. The progress that has been made in the application of electrochemical measurement to monitor and control flotation plants is also considered.

Process mineralogy as a key factor affecting the flotation kinetics of copper sulfide minerals

The aim of this study is to apply process mineralogy as a practical tool for further understanding and predicting the flotation kinetics of the copper sulfide minerals. The minerals' composition and association, grain distribution, and liberation within the ore samples were analyzed in the feed, concentrate, and the tailings of the flotation processes with two pulp densities of 25 wt% and 30 wt%. The major copper-bearing minerals identified by microscopic analysis of the concentrate samples included chalcopyrite(56.2 wt%), chalcocite(29.1 wt%),covellite(6.4 wt%), and bornite(4.7 wt%). Pyrite was the main sulfide gangue mineral(3.6 wt%) in the concentrates. A 95% degree of liberation with d_(80) > 80 μm was obtained for chalcopyrite as the main copper mineral in the ore sample. The recovery rate and the grade in the concentrates were enhanced with increasing chalcopyrite particle size. Chalcopyrite particles with a d_(80) of approximately 100 μm were recovered at the early stages of the flotation process. The kinetic studies showed that the kinetic second-order rectangular distribution model perfectly fit the flotation test data. Characterization of the kinetic parameters indicated that the optimum granulation distribution range for achieving a maximum flotation rate for chalcopyrite particles was between the sizes 50 and 55 μm.

Preliminary examination of electrochemical and spectroscopic features of trithiocarbonate collectors for sulfide mineral flotation

The redox potentials of xanthate/dixanthogen (dithiocarbonate/di dithiocarbonate, DTC/(DTC) 2) and trithiocarbonate/di trithiocarbonate (TTC/(TTC) 2) couples have been measured for the potassium salts. The spectroscopic characteristics of these sulfide mineral collectors were determined by FTIR and UV analysis. Electrochemically controlled contact angle measurements at a pyrite surface provided the basis to analyze the effect of the functional group ( O CS 2 versus S CS 2) on the hydrophobic surface state. Results from this preliminary examination are discussed with respect to the nature of collector adsorption and the pyrite flotation response.

Typical roles of metal ions in mineral flotation:A review

In flotation,metal ions possess significant roles that are usually fulfilled by either selectively activating or depressing the target minerals.Despite that tremendous efforts have been made to address the roles of metal ions in flotation,it still lacks a comprehensive review,especially to compare various ions instead of focusing on a specific one.This review begins by elaborately categorizing the factors involved in affecting the roles of metal ions in flotation.After that,well-accepted mechanisms are updated and discussed from the ore type.Furthermore,typical approaches to explore the underlying mechanisms are emphasized,including traditional techniques such as micro-flotation,contact angle measurement,zeta potential measurement,and other recent prevailing methodologies,like computational method,solution chemistry calculation,and cyclic voltammetry.This work will pave the way to promote flotations via activities like selectively adding/reducing metal ions,choosing reagents,and regulating the slurry chemistry.

New influence factor inducing difficulty in selective flotation separation of Cu–Zn mixed sulfide minerals

Selective flotation separation of Cu-Zn mixed sulfides has been proven to be difficult. Thus far, researchers have found no satis- factory way to separate Cu-Zn mixed sulfides by selective flotation, mainly because of the complex surface and interface interaction mecha- nisms in the flotation solution. Undesired activation occurs between copper ions and the sphalerite surfaces. In addition to recycled water and mineral dissolution, ancient fluids in the minerals are observed to be a new source of metal ions. In this study, significant amounts of ancient fluids were found to exist in Cu-Zn sulfide and gangue minerals, mostly as gas-liquid fluid inclusions. The concentration of copper ions re- leased from the ancient fluids reached 1.02 × 10-6 tool/L, whereas, in the cases of sphalerite and quartz, this concentration was 0.62 ×10-6 mol/L and 0.44 × 10-6 mol/L, respectively. As a result, the ancient fluid is a significant source of copper ions compared to mineral dissolution under the same experimental conditions, which promotes the unwanted activation of sphalerite. Therefore, the ancient fluid is considered to be a new factor that affects the selective flotation separation of Cu-Zn mixed sulfide ores.

Flotation of copper oxide minerals:A review

Copper oxide minerals are important copper resources,which include malachite,azurite,chrysocolla,cuprite,etc.Flotation is the most widely used method for the enrichment of copper oxide minerals in the mineral processing industry.In this paper,the surface properties of copper oxide minerals and their effects on the mineral flotation behavior are systematically summarized.The flotation methods of copper oxide minerals and the interaction mechanism with reagents are reviewed in detail.Flotation methods include direct flotation(using chelating reagents or a fatty acid as collector),sulfidization flotation(using xanthate as collector),and activation flotation(using chelating reagents,ammonium/amine salts,metal ions,and oxidant for activation).An effective way to realize efficient flotation of copper oxide minerals is to increase active sites on the surface of copper oxide minerals to enhance the interaction of collector with the mineral surface.Besides,various perspectives for further investigation on the efficient recovery of copper oxide minerals are proposed.

A new synthetic chelating collector for the flotation of oxidized-lead mineral

A new synthetic reagent DPTUHP [diphenyl α-（3-phenylthioureido） hexylpbosphonate] containing a hydrocarbon chain nonpolar group, a thioureido, and a phosphonate easter chelating group, has proven to be an effective collector for the flotation of cerussite mineral. The synthetic method utilized the Mannich-type reaction of an N-monosubstituted thiourea, an aldehyde, and triphenyl phosphate in glacial acetic acid solution. The experimental results of flotation of the cerussite mineral show that the collector has stronger collecting ability and higher selectivity in a neutral and a slightly alkaline medium, especially in the pulp of pH=8. Using the measurements by infrared spectroscopy （IR） and X-ray photoelectron spectroscopy （XPS） of the cerussite mineral, the collector, as well as the cerussite treated with the collector, the flotation mechanism of cerussite has been discussed. It is concluded that the adsorption of collector on cerussite is a chemical adsorption through the electron donor atoms of the collector chelating the Pb （ Ⅱ ） of cerussite to form chelate.

Effect of quaternary ammonium salts on flotation behavior of aluminosilicate minerals

The electrokinetic properties and flotation of diaspore, kaolinite, pyrophyllite and illite with quaternary ammonium salts collectors were studied. The results of flotation tests show that the collecting ability of quaternary ammonium salts for the four minerals is in the order（from strong to weak） ofoctadecyl dimethyl benzyl ammonium chloride（ODBA）, cetyl trimethyl ammonium bromide（CTAB）, dodecyl trimethyl ammonium chloride（DTAC）. Under the condition of alkalescence, it is possible to separate the diaspore from the silicate minerals such as kaolinite, illite and pyrophyllite using quaternary ammonium salts as collector. Isoelectric points （IEP） of diaspore, kaolinite, pyrophyllite and illite are pH=6.0, 3.4, 2.3 and 3.2, respectively. Quaternary ammonium salts can change ζ-potential of the aluminosilicate minerals obviously. The flotation mechanisms were explained by ζ-potential and Fourier transform infrared spectrum （FT-IR） measurements. The results demonstrate that only electrostatic interaction takes place between aluminosilicate minerals （diaspore, kaolinite, pyrophyllite and illite） and quaternary ammonium salts.

Flotation Separation on Rare Earth Minerals and Gangues

The flotation process of native rare earth minerals such as bastnasite, monazite, mixed minerals of bastnasite and monazite, using the new effective collector Dh was studied, respectively, and the flotation properties were described. The good qualities of the new collector Dh were revealed through comparing with other collector of rare earth minerals. The test results of different ore samples showed that at moderate pulp pH (8.5～9.5), rare earth minerals could be effectively separated from barium, calcium and silicon bearing intergrowth minerals (barite, calcite and silicate minerals) and high quality rare earth concentrates could be obtained successfully by the new collector Dh, acid silica gel, turpentine and reagents fitting together rationally. In order to determine optimum technical conditions, the effect of pulp pH, pulp temperature, pulp density and the effect of dosage of reagents (Dh and acid silica gel) on the flotation were investigated in the test. Simultaneously, the mechanism of the flotation of rare earth minerals from intergrowth minerals was explored. The infrared spectra for Dh and rare earth cation by analysis in theory showed that Dh formed chelate complex with rare earth cation and were adsorbed on the surfaces of rare earth minerals. The mechanism of the intergrowth minerals depressed by acid silica gel can be explained as gummy colloid hydrolyzed from acid silica gel which were selectively absorbed on the gangue minerals, making them hydrophilic and depressed, with pulp pH value of alkalescent.

Latest advances and progress in the microbubble flotation of fine minerals:Microbubble preparation,equipment,and applications

In the past few decades,microbubble flotation has been widely studied in the separation and beneficiation of fine minerals.Compared with conventional flotation,microbubble flotation has obvious advantages,such as high grade and recovery and low consumption of flotation reagents.This work systematically reviews the latest advances and research progress in the flotation of fine mineral particles by microbubbles.In general,microbubbles have small bubble size,large specific surface area,high surface energy,and good selectivity and can also easily be attached to the surface of hydrophobic particles or large bubbles,greatly reducing the detaching probability of particles from bubbles.Microbubbles can be prepared by pressurized aeration and dissolved air,electrolysis,ultrasonic cavitation,photocatalysis,solvent exchange,temperature difference method(TDM),and Venturi tube and membrane method.Correspondingly,equipment for fine-particle flotation is categorized as microbubble release flotation machine,centrifugal flotation column,packed flotation column,and magnetic flotation machine.In practice,microbubble flotation has been widely studied in the beneficiation of ultrafine coals,metallic minerals,and nonmetallic minerals and exhibited superiority over conventional flotation machines.Mechanisms underpinning the promotion of fine-particle flotation by nanobubbles include the agglomeration of fine particles,high stability of nanobubbles in aqueous solutions,and enhancement of particle hydrophobicity and flotation dynamics.

Effect of mineral processing wastewater on flotation of sulfide minerals

The effects of mineral processing wastewater on sulfide minerals were investigated by flotation,infrared spectrometry and electrochemistry test. The results show that lead-concentrate water can improve the flotation of galena,while the sulfur-concentrate water has negative effect on flotation of galena compared with distilled water. The flotation behavior of pyrite is contrary to that of galena in three kinds of water. Infrared spectra indicate that the residual collector in the lead-concentrate water is beneficial to the formation of lead xanthate on the surface of galena. Electrochemistry results indicate that electrochemistry reaction on galena surface has apparent change. The anode polarization is improved and cathode polarization is depressed.

Solution chemistry of carbonate minerals and its effects on the flotation of hematite with sodium oleate

The effects of carbonate minerals（dolomite and siderite） on the flotation of hematite using sodium oleate as a collector were investigated through flotation tests, supplemented by dissolution measurements, solution chemistry calculations, zeta-potential measurements, Fourier transform infrared（FTIR） spectroscopic studies, and X-ray photoelectron spectroscopy（XPS） analyses. The results of flotation tests show that the presence of siderite or dolomite reduced the recovery of hematite and that the inhibiting effects of dolomite were stronger. Dissolution measurements, solution chemistry calculations, and flotation tests confirmed that both the cations（Ca^（2＋） and Mg^（2＋）） and CO_3^（2＋）ions dissolved from dolomite depressed hematite flotation, whereas only the 23CO-ions dissolved from siderite were responsible for hematite depression. The zeta-potential, FTIR spectroscopic, and XPS analyses indicated that Ca^（2＋）, Mg^（2＋）, and CO_3^（2-）（HCO_3^-） could adsorb onto the hematite surface, thereby hindering the adsorption of sodium oleate, which was the main reason for the inhibiting effects of carbonate minerals on hematite flotation.

Galvanic coupling and its effect on origin potential flotation system of sulfide minerals

The galvanic coupling formed in origin potential flotation systems of sulfide minerals can be divided （into） three types: sulfide mineral-sulfide mineral-water system; sulfide mineral-steel ball-water system; and sulfide mineral-sulfide mineral-collector system. In this paper, taking lead, zinc, iron sulfide mineral systems for examples, several models of galvanic coupling were proposed and the effects of galvanic coupling on flotation were discussed. A galvanic contact between galena （or sphalerite） and pyrite contributes to decreasing the content of zinc in lead concentrate, and enhances remarkably the absorption of collector on the galena surface. During grinding, due to galvanic interactions between minerals and steel medium, Fe（OH）3 formed covers on the cathodic mineral surface, affecting its floatability.

STUDY ON INTERACTION ENERGY BETWEEN FLOTATION REAGENT AND MINERAL SURFACE

The interaction between a flotation reagent and mineral surface not only depends on the bonding atom, but also depends on the adjacent atom of mineral surface, a flotation reagent and the medium in the system of flotation. Energy equation of a reagent interacting with mineral surface has been deduced from this model. Results of the studies indicate that the interaction energy between mineral surface and a reagent is about several dozen kJ/mol, and the relationship between adsorbing concentration of xanthate on mineral surface and interaction energy is the exponent form.

Flotation separation depressants for scheelite and calcium-bearing minerals: A review

Owing to the depletion of wolframite, the focus of tungsten extraction has gradually shifted to scheelite. However, separating the associated minerals(e.g., apatite, fluorite, and calcite) and scheelite is challenging because their surface physicochemical properties are similar to those of scheelite. Fortunately, researchers have made substantial progress in separating the minerals of scheelite by using depressants. This study reviews the application and inhibition mechanism of inorganic depressants in obtaining tungsten from its calcium-bearing minerals. The application of new organic depressants in obtaining tungsten from its calcium-bearing minerals and the associated mechanisms are also summarized. After an objective assessment of inorganic and organic depressants’ advantages and disadvantages, possible future research directions for inorganic and organic depressants are proposed. Herein, we provide a theoretical basis for developing scheelite flotation depressants.

EFFECTS OF DISSOLVED MINERAL SPECIES ON THE SURFACE CHEMICAL CHARACTERISTIC,ELECTROKINETIC PROPERTY AND FLOTATION BEHAVIOR OF FLUORITE AND SCHEELITE

Interactions between the dissolved mineral species and other mineralsurface were investigated using solution chemistry calculation, -potential measurement, AES analysis and flotation tests. It has been indicated that there canbe precipitation of scheelite over fluorite in scheelite supernatant at PH> 4.The conversion of fluorite into scheellte was detected by AES. Fluorite in the supernatant of scheelite exhibits nearly identical electrokinetic property andflotation behavior with those of scheelite. The selective flotatlon separation of fluorite from scheelite or vice vasa may be achieved by using selective amphoteric collector for fluorite at PH<4 to avoid surface conversion.

Progress of Flotation Reagents of Rare Earth Minerals in China

The development and application of several flot ation reagents of rare earth minerals in China since 1960s and their performance were described. Furthermore, the development trends of flotation reagents of ra re earth minerals were discussed.

Physical chemistry mechanisms of CDR system in sulphide mineral flotation

The flotation tests, zeta potential measurements, and Fourier transform infrared spectroscopy （FTIR） analysis on galena, sphalerite, and pyrite were studied in a collecting-depressing-reactivating （CDR） system. In this system, sulphide minerals were first collected and acti- vated by the collector, and then depressed strongly by Ca（OH）2 in a strong alkaline solution. Finally, they were reactivated by H2SO4. The flotation tests of pure minerals showed that in the Ca（OH）2 depressing process sulphide minerals had similar flotation characteristics because they had already been influenced by the collector. Hence, the flotability differences between them were reduced. However, in the H2SO4 re- activating process considerable differences in the flotability between galena and sphalerite/pyrite were produced. That is to say, galena was relatively easy to be reactivated by H2SO4, but sphalerite and pyrite were not reactivated at pH 〉 11. The zeta potentials of sulfide minerals measured by the Zeta Plus presented irreversible characteristics on the change of pH values. The results of the FTIR spectra analysis indi- cated that the collectors already adsorbed on the mineral surface were removed partially by Ca（OH）〉