A review of flotation and selective separation of pyrrhotite:A perspective from crystal structures

Pyrrhotite is an associated mineral that exists widely in sulfide ore. The presence of pyrrhotite will affect the recovery of platinum group minerals. Therefore, researchers have paid increasing attention to the flotation separation of pyrrhotite. Pyrrhotite superstructures owning different Fe/S ratios results in various crystal structures, corresponding to different physical, chemical and electronic properties, and consequently different flotation behavior. In the present paper, a comprehensive review is conducted to discuss the influence of crystal structures on the natural floatability, mineral-reagent interaction, surface oxidation and flotation electrochemistry of pyrrhotite. The selective flotation process of pyrrhotite from its associated minerals is also reviewed in this paper. It is hoped that this review can summarize the newly published research results combined with some representative results from the past, to provide a theoretical basis for the study of the flotation mechanism of pyrrhotite and provide a new direction for future research on pyrrhotite.

The selective effect of food-grade guar gum on chalcopyrite-monoclinic pyrrhotite separation using mixed aerofloat(CSU11) as collector

The flotation separation of chalcopyrite from monoclinic pyrrhotite using food-grade guar gum(FGG) as a depressant was studied through flotation tests, kinetic studies, dynamic potential measurements, adsorption experiments, and infrared spectral analyses. The microflotation results showed that the flotation separation of chalcopyrite from monoclinic pyrrhotite could not be realized by adding mixed aerofloat(CSU11) alone. The depressant FGG exhibited a selective depression effect on monoclinic pyrrhotite by controlling the pulp pH range from 5.0 to 6.0, with a maximum floatability variation of 79.36% in the presence of CSU11. The flotation kinetics, zeta-potential, adsorption, and infrared spectroscopy studies revealed that the FGG could absorb more strongly on the surface of monoclinic pyrrhotite than on the surface of chalcopyrite. In addition, the results revealed that the interaction of FGG with the monoclinic pyrrhotite surface was governed primarily by strong chemisorption, whereas FGG mainly bonded to chalcopyrite through hydrogen bonding. This difference was responsible for the excellent depression selectivity of FGG toward monoclinic pyrrhotite flotation and weak depression effect toward chalcopyrite flotation.

A study of self-heating characteristics of a pyrrhotite-rich sulphide ore stockpile

Original surface chemistry of sulphidesis altered upon contact with air, leading to ''oxidation'', which is accompanied by evolution of heat. The current study reports results of an investigation on extent of exothermicity of an experimental nickel-copper sulphide stockpile that was formed at a mining site in Sudbury, Canada. The ore contained pentlandite and chalcopyrite that are accompanied by a large quantity of pyrrhotite. The self-heating characteristics were recorded by temperature sensors placed inside the stockpile. Ambient conditions such as temperature, humidity, and wind velocity were simultaneously recorded. The inner temperature of the stockpile indicated significant fluctuations due to rapid changes, particularly in the outside temperature. The minimum and maximum temperatures recorded in the outside and inside were 5 and 10.5, 44.3 and 32 ℃, respectively. The self-heating capacity of the sulphide ore stockpile observed represents a mild case compared to that experienced by coals. Possible reasons are discussed.

Electrochemical flotation separation of marmatite from pyrrhotite in the presence of copper ion

In the presence of Cu 2+ ion, and pH range of 2.0 to 12.0, the floatability of pyrrhotite and marmatite is well, so marmatite can not be separated from pyrrhotite. The technique of electrochemical flotation was used to separate marmatite from pyrrhotite in the presence of Cu 2+ . Pyrrhotite can be depressed and marmatite be floated through controlling the potential of flotation. Marmatite can be separated from pyrrhotite in the pulp potential range of -0.25 V to 0 V (vs SHE) at pH11.2 solution. The chronopotentiometry results of pyrrhotite and marmatite in the presence of Cu 2+ and butyl xanthate showed that, when the pH is 11.2 and the pulp potential is -0.2 V (vs SHE), the CuX 2 is adsorbed on marmatite surface, and the dixanthogen adsorbed on pyrrhotite surface is reduced.

Kinetics and mechanism of oxidation for nickel-containing pyrrhotite tailings

X-ray powder diffraction,scanning electron microscopy,energy dispersive spectroscopy,thermogravimetry,differential scanning calorimetry,and mass spectrometry have been used to study the products of nickel-containing pyrrhotite tailings oxidation by oxygen in the air.The kinetic triplets of oxidation,namely,activation energy(E_(a)),pre-exponential factor(A),and reaction model(f(α))being a function of the conversion degree(α),were adjusted by regression analysis.In case of a two-stage process representation,the first step proceeds under autocatalysis control and ends atα=0.42.The kinetic triplet in the first step is E_(a)=262.2 kJ/mol,lg A=14.53 s^(−1),and f(α)=(1-α)^(4.11)(1+1.51×10^(-4)α).For the second step,the process is controlled by the two-dimensional diffusion of the reactants in the layer of oxidation products.The kinetic triplet in the second step isЕa=215.0 kJ/mol,lg A=10.28 s^(−1),and f(α)=(-ln(1-α))^(-1).The obtained empirical formulae for the rate of pyrrhotite tailings oxidation reliably describe the macro-mechanism of the process and can be used to design automatization systems for roast-ing these materials.

Electrodeposition of dixanthogen on surface of pyrrhotite electrode

Electrochemical behavior of pyrrhotite in the presence of xanthate solution was studied. Cycle voltammogram scan, chronopotentiometry and rotating disc electrode measurements were used to analyze the electrodeposit process of dixanthogen on the surface of pyrrhotite electrode. Experimental results demonstrate that the first step of electrodeposit is electrochemical adsorption of xanthate ion, and then one xanthogennic ion adsorbed integrates itself with another free xanthate ion to form dixanthogen. Using galvanostatic technique, the electrochemical dynamics equation of the electrodeposit process of dixanthogen on the surface of pyrrhotite electrode was set up. It can quantitatively describe the oxidation process of xanthate on pyrrhotite surface.

Desulfurization of Nickel Pyrrhotite by Steam in the Microwave Field

Desulfurization of Ni pyrrhotite by steam in the microwave field was studied. According to the experimental data, the desulfurization rate by microwave heating is faster than that by conventional one. The desulfurization reaction is in a non-isothermal state and in a diffusion control because of the effect of chemical reaction heat, phase formation and intrinsic properties of materials of microwave absorbability. When the flow rate of steam was in the range of 180 similar to 220 mL/min, the temperature and desulfurization rate approached to a maximum and the activation energy to a minimum.

One-step disposal of Cr (Ⅵ)-bearing wastewater by natural pyrrhotite

Cr(Ⅵ)-bearing wastewater can be treated by natural pyrrhotite which is used for reductant to reduce Cr(Ⅵ) and precipitant to precipitate Cr(Ⅲ) simultaneously. The disposal products can be divided into three parts in the beakers, namely supernatant in the upper part, the yellowish colloidal precipitates in the middle part and the pyrrhotite in the lower part. The content of total Cr=Cr(Ⅵ)+Cr(Ⅲ) in the supernatant liquid is 0.06 mg/L, which is lower than 1.5 mg/L of the discharge standard of China and near to 0.05 mg/L of the standard of potable water. This one-step disposal composing of both reduction and precipitation which is traditionally divided into two independent steps called reducing technology and precipitating technology respectively. The new method is of obvious economic advantage and favourable to decreasing surplus mud derived from adding Ca(OH)2 to precipitate Cr(Ⅲ) traditionally so as to avoid recontamination. In fact, sodium sulfite (Na2SO3) used in disposal of Cr(Ⅵ) was

Isothermal Kinetics of the Pentlandite Exsolution from mss/Pyrrhotite Using Model-Free Method

The pentlandite exsolution from monosulfide solid solution （mss）/pyrrhotite exsolution is a complex multi-step process, including nucleation, new phase growth and atomic diffusion, and lamellae coarsening. Some of these steps occur in sequence, others simultaneously. These make its kinetic analysis difficult, as the mechanisms cannot be elucidated in detail. In mineral reactions of this type, the true functional form of the reaction model is almost never known, and the Arrhenius parameters determined by the classic Avrami method are skewed to compensate for errors in the model. The model-free kinetics allows a universal determination of activation energy. Kinetic study of pentlandite exsolution from mss/pyrrhotite was performed over the temperature range 200 to 300℃. For mss/pyrrhotite with bulk composition （Fe0.77Ni0.19）S, activation energy of pentlandite exsolution, Ea, varies from 49.6 kJ · mol^-1 at the beginning of reaction （nucleation is dominant） to 20.7 kJ · mol^-1 at the end （crystal growth is dominant）. In general, the activation energy varies during the course of solid reaction with the extent of reaction. The surrounding environment of reactant atoms affects the atom＇s activity and more or less accounts for changes of activation energy Ea.

Improvement of hydrogen permeation barrier performance by iron sulphide surface films

Fe–S compounds with hexagonal crystal structure are potential hydrogen permeation barrier during H2S corrosion. Hexagonal system Fe–S films were prepared on carbon steel through corrosion and CVD deposition, and the barrier effect of different Fe–S films on hydrogen permeation was tested using electrochemical hydrogen permeation method. After that, the electrical properties of Fe–S compound during phase transformation were measured using thermoelectric measurement system. Results show that the mackinawite has no obvious barrier effect on hydrogen penetration, as a p-type semiconductor, and pyrrhotite (including troilite) has obvious barrier effect on hydrogen penetration,as an n-type semiconductor. Hydrogen permeation tests showed peak permeation performance when the surface was deposited with a continuous film of pyrrhotite (Fe_(1–x)S) and troilite. The FeS compounds suppressed hydrogen permeation by the promotion of the hydrogen evolution reaction, semiconducting inversion from p-to n-type, and the migration of ions at the interface.

Environmental Properties of Minerals and Contaminants Purified by the Mineralogical Method

The investigation of the environmental properties of minerals, i.e., environmental mineralogy, is a branch of science dealing with interactions between natural minerals and spheres of the Earth surface as well as a reflection of global change, prevention of ecological destruction, participation in biomineralogy, and remediation of environmental pollution. Pollutant treatment by natural minerals is based on the natural law and reflects natural self-purification functions in the inorganic world, similar to that of the organic world - a biological treatment. A series of case studies related to natural self-purification, which were mostly completed by our group, are discussed in this paper. In natural cryptomelane there is a larger pseudotetragonal tunnel than that formed by [MnO6] octahedral double chains, with an aperture of 0.462-0.466 nm2, filled with K cations. Cryptomelane might be a real naturally-occurring mineral of the active octahedral molecular sieve (OMS-2). CrⅥ-bearing wastewater can be treated by natural pyrrhotite, which is used as a reductant to reduce CrⅥ and as a precipitant to precipitate CrⅢ simultaneously. Batch experiments were conducted using the CTMAB-Montmorillonite as an adsorbent for aromatic contaminants (phenol, aniline, benzene, toluene and xylenes), which are detected frequently in the leaching water from municipal waste deposits around China. The CTMAB modification has proved very effective to enhance the adsorption capacity of the sorbent. Expansion of vermiculite develops loose interior structures, such as pores or cracks, inside briquettes, and thus brings enough oxygen for combustion and the sulfation reaction. Effective combustion of the original carbon reduces the amount of dust in the fly ash.

Zinc bioleaching from an iron concentrate using Acidithiobacillus ferrooxidans strain from Hercules Mine of Coahuila,Mexico

The iron concentrate from Hercules Mine of Coahuila,Mexico,which mainly contained pyrite and pyrrhotite,was treated by the bioleaching process using native strain Acidithiobacillus ferrooxidans （A.ferrooxidans） to determine the ability of these bacteria on the leaching of zinc.The native bacteria were isolated from the iron concentrate of the mine.The bioleaching experiments were carried out in shake flasks to analyze the effects of pH values,pulp density,and the ferrous sulfate concentration on the bioleaching process.The results obtained by microbial kinetic analyses for the evaluation of some aspects of zinc leaching show that the native bacteria A.ferrooxidans,which is enriched with a 9K Silverman medium under the optimum conditions of pH 2.0,20 g/L pulp density,and 40 g/L FeSO4,increases the zinc extraction considerably observed by monitoring during15 d,i.e.,the zinc concentration has a decrease of about 95% in the iron concentrate.

Environmental boundary and formation mechanism of different types of H2S corrosion products on pipeline steel

To establish an adequate thermodynamic model for the mechanism of formation of hydrogen sulfide(H_2S) corrosion products,theoretical and experimental studies were combined in this work. The corrosion products of API X60 pipeline steel formed under different H_2S corrosion conditions were analyzed by scanning electron microscopy,energy-dispersive X-ray spectroscopy,and X-ray diffraction. A thermodynamic model was developed to clarify the environmental boundaries for the formation and transformation of different products. Presumably,a dividing line with a negative slope existed between mackinawite and pyrrhotite. Using experimental data presented in this study combined with previously published results,we validated the model to predict the formation of mackinawite and pyrrhotite on the basis of the laws of thermodynamics. The established relationship is expected to support the investigation of the H_2S corrosion mechanism in the oil and gas industry.

Chemical Enrichment of Nickel Sulfide

The availability of polymetallic ores is getting leaner in grade and is larger but inferior in volumes than in the past, making the extraction of copper, nickel and other non-ferrous metals metallurgically more difficult to produce. The standard technologies, including enrichment and concentration, do not provide methods for obtaining monometallic concentrates and high extraction of metals into the commercial product. Pyrometallurgical processing of large volumes of poor raw materials is not economical and is complicated from the technological point of view. Conditions of chemical enrichment of poor natural materials have been studied with the use of technology of salt exchange leaching. The main impurity in sulfide ores of nonferrous metals is iron present in the forms of pyrite and pyrrhotite and the properties of chemical enrichment for nickel in pyrite concentrates has been investigated in this work. On the basis of thermodynamic analysis carried out with the use of Potential-pH Pourbaix’s Diagrams, it has been established that, with the use of nickel salt, it is possible to leach iron sulfides from ores. Based on the study of the mechanism and kinetics of the process of dissolution of iron sulfides with nickel salts, it was established that during the dissolution, the chemical composition and thermodynamic characteristics of the dissolved iron sulfides change—the residues from leaching are enriched with iron sulfides that are rich in sulfur and also result with elemental sulfur formation. Enrichment of leaching residues with sulfide iron with increased sulfur content and formation on the surface of nickel sulfide leads to increase of diffusional resistances and the process is limited by the velocity of mass transfer. To increase the velocity of the process and completeness of the reaction, it is necessary to activate the process, in particular, by grinding the solid phase.

Magnetic properties related to thermal treatment of pyrite

Detailed rock magnetic experiments were conducted on high-purity natural crystalline pyrite and its products of thermal treatments in both argon and air atmospheres. In argon atmosphere (reducing environment), the pyrite is altered by heating to magnetite and pyrrhotite; the latter is stable in argon atmosphere, and has coercive force and coercivity of remanence of ～20 and ～30 mT, respectively. Whereas in air, the pyrite is ultimately oxidized to hematite. First order reversal curve (FORC) diagram of the end product shows that the remanence coercivity of hematite is up to ～1400 mT. The corresponding thermal transformation process of pyrite in air can be simply summarized as pyrite→ pyrrhotite→magnetite→hematite. These results are helpful for understanding of sedimentary magnetism, secondary chemical remanence and meteorolite magnetic properties.

Complex exsolution in Te minerals from the Dashuigou Te deposit

The Dashuigou Te deposit, Sichuan Province, is a unique independent one found up to date in the world. During the mineralogical study of this deposit, the authors observed a number of small vermicular, linear or lamellar minerals in the tsumoite. Such a complex exsolution phenomenon is noted for the first time in Te minerals. The assemblage of tsumoite + exsolution is named complex exsolution zone. We will make detailed study on this exsolution structure and discuss its origin.