Mineral activation, sphalerite

Aetivators. These are used to make a mineral surface amenable to collector coating. Copper ion is used, for example, to activate sphalerite (ZnS), rendering the sphalerite surface capable of absorbing a xanthate or dithiophosphate collector. Sodium sulfide is used to coat oxidized copper and lead minerals so that they can be floated by a sulfide mineral collector. 

The copper sulfide formed on the surface of the sphalerite mineral reacts readily with the xanthate, and forms insoluble copper xanthate, which makes the sphalerite surface hydro-phobic. Such a reaction for activating sphalerite occurs whenever the activating ions are present in the solution. It is thus necessary to deactivate sphalerite (to prevent the occurrence of natural activation) in the case of some ores. With lead-zinc ores, for example, natural activation occurs due to Pb2+ in solution... 

A deactivating agent for copper-activated sphalerite is any species that has sufficient affinity for copper(I) or (II) to compete for it with sulfide ions in the surface lattice of the mineral, thus removing it from the surface. Ligands such as cyanide or ethylenediamine, which coordinate strongly to copper, have therefore been found to be the most effective. A knowledge of the stability of the species present in a system composed of and CN ions has enabled ... 

T. N. Khmeleva, W. Skinner, and D. A. Beattie, Depressing mechanisms of sodinm bisulphite in the coUectorless flotation of copper-activated sphalerite, Internat. J. Mineral Processing 76(1-2) (2005). 

The galena would be floated first under conditions of alkaline pH (pH 8-10) using a low concentration of an alkyl xanthate as the collector, sodium sulfite to depress the zinc minerals and a short-chain alcohol as a frother. After galena flotation, the pH would be raised to 11-12 (to depress gangue iron sulfides) copper sulfate is added to activate sphalerite and marmatite additional alkyl xanthate is added to float these two minerals. The final lead concentrate should be more than half lead with minimal zinc content the final zinc concentrate should be more than half zinc with minimal lead content. 

Leppinen [483] studied the adsorption of EX on nonactivated pyrite, pyrrhotite, chalchopyrite, and sphalerite and on the same minerals activated with copper sulfate. He used the particle-bed electrode (Fig. 4.51) [513, 514] under open-circuit conditions. The IR results were compared to the flotation data. Dixanthogen was found on nonactivated pyrite, pyrrhotite, and chalchopyrite. Iron xanthate... 

Activators enhance the adsorption of collectors, eg, Ca " in the fatty acid flotation of siUcates at high pH or Cu " in the flotation of sphalerite, ZnS, by sulfohydryl collectors. Depressants, on the other hand, have the opposite effect they hinder the flotation of certain minerals, thus improving selectivity. For example, high pH as well as high sulfide ion concentrations can hinder the flotation of sulfide minerals such as galena (PbS) in the presence of xanthates (ROCSS ). Hence, for a given fixed collector concentration there is a fixed critical pH that defines the transition between flotation and no flotation. This is the basis of the Barsky relationship which can be expressed as [X ]j[OH ] = constant, where [A ] is the xanthate ion concentration in the pulp and [Oi/ ] is the hydroxyl ion concentration indicated by the pH. Similar relationships can be written for sulfide ion, cyanide, or thiocyanate, which act as typical depressants in sulfide flotation systems. 

Activators promote the reaction of the coUector with some minerals. For example, ordinarily xanthates do not bind to sphalerite, but pretreatment of the sphalerite using copper sulfate enables it to adsorb the xanthate. Thus it is possible to float the sphalerite from lead—zinc ores after the galena has been recovered. 

Figure 1.96. Log /oj-pH diagram constructed for temperature = 200°C, ionic strength = 1, ES = 10 m, and EC = 10 m. Solid line represents aqueous sulfur and carbon species boundaries which are loci of equal molalities. Dashed lines represent the stability boundaries for some minerals. Ad adularia. Bn bomite, Cp chalcopyrite, Ht hematite, Ka kaolinite, Mt magnetite, Po pyrrhotite, Py pyrite, Se sericite. Heavy dashed lines (1), (2), and (3) are iso-activity lines for ZnCOs component in carbonate in equilibrium with sphalerite (1) 4 co3=0-1- (2) 4 ,co3=0-01- (3) 4 co3 =0-001 (Shikazono, 1977b).

Opaque minerals identified from active geothermal areas are pyrite, sphalerite, galena, chalcopyrite, and tetrahedrite from Okuaizu, Fushime, and Nigorikawa (Japan), Salton Sea (U.S.A.) and Broadlands (New Zealand). 

Activators are those reagents which act in a manner converse to the action of depressants, i.e., they render those minerals floatable which either have been temporarily depressed or would not float without their assistance. They are generally soluble salts which ionize in the aqueous medium. The ions then react with the mineral surface, providing a monomolecular coating and thereby making the mineral surface favourably disposed to the collectors. Sphalerite (ZnS) is essentially not floatable with common collectors. The addition of Cu2+ to the solution, however, alters the mineral surface to CuS, which can adsorb collector. This feature is described elaborately in a later section. 

The flotation of sphalerite, the sulfidic mineral source of zinc, is next considered as an example to illustrate the role of activators. This mineral is not satisfactorily floated solely by the addition of the xanthate collector. This is due to the fact that the collector products formed, such as zinc xanthate, are soluble in water, and so do not furnish a hydrophobic film around the mineral particles. It is necessary to add copper sulfate which acts as an... 

The mineral, sphalerite, on account of its resistance to oxidation, contributes very little of Zn2+ through dissolution. In this case, zinc sulfate is added and the reaction, which is shown in the parenthesis, is pressed into proceeding from right to left (i.e., PhS + Zn2+ —> ZnS +Pb2+). This is equivalent to saying deactivation of sphalerite. Besides Pb2+, Cu2+ is also known to give rise to activation. In this case, cyanide ions are introduced into the system. The stability of Cu(CN)2, relative to Zn(CN)2- results in ratios of dissolved Cu to Zn such that activation cannot occur. 

Several reviews on ore processing by flotation are available.17-21 In addition to providing details of the chemistry of collectors they describe the use of activators and depressants. The former usually convert the surfaces of an ore particle which does not bind strongly to conventional collectors to one that does. The addition of Cu2+ ions to enhance the flotability of minerals such as sphalerite, a zinc sulfide, has been exploited for some time.4 Formation of a surface layer of CuS has been assumed to account for this, but the mechanisms and selectivities of such processes continue to be investigated.18,22,23... 

Figures 8.25, 8.26, 8.27 and 8.28 are surface appearance of sphalerite at original state, and ground by coarse media, middling media and fine media, respectively. The figures above show that sphalerite has similar changes to those of pyrite under the four different conditions except that the colorization of sphalerite surface is not as evident as that of pyrite under the fine grinding condition. It indicates that there may be more active species to be formed on the surface of pyrite than sphalerite. This is consistent with the findings from the previous researches that among the three sulphide minerals the pyrite erodes are the fastest and its eroding current is the largest.

In flotation, when sphalerite is activated by Cu or Fe the ZnS surface will exhibit good reactivity to organic collector. Our calculation shows that when the surface is doped by transition metal ions, the surface ions will be rendered more ionic property, which benefits the interaction between the mineral surface and the collector anions. It gives more profoimd explanation for Cu activated behavior to ZnS. 

Fereshteh, R., Caroline, S., James, A. F., 2002. Sphalerite activation and surface Pb ion concentration. Inter. J. Miner. Process, 67 43 - 58 Fierro, R. E., Tryk, D., Scherson, D., Yeager, E., 1988. Perovskite-type oxides oxygen electrocatalysis and bulk structure. Journal of Power Sources, 22 (3 - 4) 387 - 398... 

Kartio, I. J., Basilio, C. I., Yoon, R. H., 1996. An XPS study of sphalerite activation by copper. In R. Woods, F. Doyle, P. E. Richardson (eds.), Electrochemistry in Mineral and Metal Processing IV. The Electro-Chemical Society, 25 - 34 Kelebek, S., 1987. Wetting behaviow, polar characteristics and flotation of inherently hydrophobic minerals. Trans. MM, Sec. C, 96 103 - 107... 

Trahar, W. J., Senior, G. D., Heyes, G. W., Creed, M. D., 1997. The activation of sphalerite by lead—a flotation perspective. Inter. J. Miner. Process, 49 121 - 148 Usui, A. H. and Tolun, R., 1974. Electrochemical study of the pyrite-oxygen-xanthate system. Inter. J. Miner. Process, 1 135 - 140... 

Zhao Jing et al., 1988. Research on the mechanism of chalcopyrite depressed by sodium mercaptoacetic. Nonferrous Metals (part of mineral processing), (3) 42 - 45 Zhuo Chen and Yoon, R. H., 2000. Electrochemistry of copper activation of sphalerite. Inter. J. Miner. Process, 58 57 - 66... 

The most widely applied activation procedure is that involving the use of copper(II) ions to enhance the floatability of some sulfide minerals, notably the common zinc sulfide mineral sphalerite.2 Sphalerite does not react readily with the common thiol collectors, but after being treated with small amounts of copper it floats readily owing to the formation of a surface layer of CuS." A similar procedure is often adopted in the flotation of pyrrhotite (FeS), pyrite (FeS2), galena (PbS) and stibnite (Sb2S3). In the context of coordination chemistry, the major contribution has been to the understanding of the chemistry involved in the deactivation of these minerals, a procedure often adopted in the sequential flotation of several minerals from a complex ore. 

The triboluminescence of minerals has been studied visually (see the footnotes to Table I) but only a few minerals have been examined spectroscopically. There are a few clear examples of noncentric crystals, such as quartz, whose emission is lightning, sometimes with black body radiation. Most of the triboluminescent minerals appear to have activity and color which is dependent on impurities, as is the case for kunzite, fluorite, sphalerite and probably the alkali halides. Table I attempts to distinguish between fracto-luminescence and deformation luminescence, but the distinctions are not clear cut. A detailed analysis of the structural features of triboluminescent and nontriboluminescent minerals may make it possible to draw conclusions about the nature and concentration of trace impurities that are not obvious from the color or geological site of the crystals. Triboluminescence could be used as an additional method for characterizing minerals in the field, using only the standard rock hammer, with the sensitive human eye as a detector. 

Quite frequently the natural surface of a mineral requires preliminary chemical treatment before it will form the surface film required for collection One of the commonest instances of this is with sphalerite (zinc sulphide), which does not float properly when treated with xanthates. If, however, it is given a preliminary treatment with dilute copper sulphate solution, a very small amount of copper sulphide is deposited on the surface and the ore becomes floatable, the surface being now capable of reaction with xanthates. Such treatment is usually termed activation in general, an activating solution for a sulphide mineral should contain a metallic ion whose sulphide is less soluble than that contained in the mineral for zinc sulphides, silver, copper, mercury, cadmium, and lead salts are all effective activators. 

There is a general consensus (vide supra) on the environmental importance of catalytic reactions on the surface of many minerals. However, there is limited information in the literature about specific examples [9]. Systematic studies would allow the understanding of the dependence of the catalytic activity on mineral structure, mineral chemistry and surface reactivity. At the same time, this knowledge would be useful in designing remediation techniques based on minerals instead of synthetic catalysts. For example, sphalerite and ilmenite have been shown to be capable of degrading chlorinated carbon compounds via a photo catalytic mechanism [63]. 

Weisener (2002) observed increased rates of oxidation and increased acid consumption as a function of the amount of solid-solution iron in sphalerite [(Zn,Fe)S]. Apparent activation energies of 21-28kJmol obtained at 25-85 °C are similar to the values reported by Rimstidt et al. (1994). Weisener et al. (2003) suggested that the production of polysulfide species results in a lower diffusion gradient at the mineral surface, thus leading to lower reactivity with potential oxidants and to diffusion-limited release of zinc and iron from the bulk mineral. Elemental sulfur was not observed to limit the reactivity of the mineral surface. The accumulation of polysulfides and S° on the sphalerite surface under oxygenated conditions can affect the acid-neutralization capacity because the polysulfides and S° consume acid when pH is <3. The resulting formation of a sulfur-enriched surface slows the subsequent rate of dissolution of sphalerite in the absence of bacteria. Under these conditions, S° does not passivate the surface (Weisener, 2002). 

---