Mineral-thio-collector

Some instrumental methods have been used for the investigation of sulphide mineral-thio-collector system such as infra-red (IR) spectroscopy (Mielezarski and Yoon, 1989 Leppinen et al., 1989 Persson et al, 1991 Laajalehto et al, 1993 Zhang., et al., 2004a) and X-ray photoelectron spectroscopy (XPS) (Pillai et al, 1983 Page and Hazell, 1989 Grano et al, 1990 Laajalechto et al, 1991). These surface sensitive spectroscopic techniques can be applied for the direct determination of the surface composition at the conditions related to flotation. 

Abstract In the beginning, the mixed potential model, which is generally used to explain the adsorption of collectors on the sulphide minerals, is illustrated. And the collector flotation of several kinds of minerals such as copper sulphide minerals, lead sulphide minerals, zinc sulphide minerals and iron sulphide minerals is discussed in the aspect of pulp potential and the nature of hydrophobic entity is concluded from the dependence of flotation on pulp potential. In the following section, the electrochemical phase diagrams for butyl xanthate/water system and chalcocite/oxygen/xanthate system are all demonstrated from which some useful information about the hydrophobic species are obtained. And some instrumental methods including UV analysis, FTIR analysis and XPS analysis can also be used to investigated sulphide mineral-thio-collector sytem. And some examples about that are listed in the last part of this chapter. 

In the 2nd period ranging from the 1930s to the 1950s, basic research on flotation was conducted widely in order to understand the principles of the flotation process. Taggart and co-workers (1930, 1945) proposed a chemical reaction hypothesis, based on which the flotation of sulphide minerals was explained by the solubility product of the metal-collector salts involved. It was plausible at that time that the floatability of copper, lead, and zinc sulphide minerals using xanthate as a collector decreased in the order of increase of the solubility product of their metal xanthate (Karkovsky, 1957). Sutherland and Wark (1955) paid attention to the fact that this model was not always consistent with the established values of the solubility products of the species involved. They believed that the interaction of thio-collectors with sulphides should be considered as adsorption and proposed a mechanism of competitive adsorption between xanthate and hydroxide ions, which explained the Barsky empirical relationship between the upper pH limit of flotation and collector concentration. Gaudin (1957) concurred with Wark s explanation of this phenomenon. Du Rietz... 

The mixed-potential model demonstrated the importance of electrode potential in flotation systems. The mixed potential or rest potential of an electrode provides information to determine the identity of the reactions that take place at the mineral surface and the rates of these processes. One approach is to compare the measured rest potential with equilibrium potential for various processes derived from thermodynamic data. Allison et al. (1971,1972) considered that a necessary condition for the electrochemical formation of dithiolate at the mineral surface is that the measmed mixed potential arising from the reduction of oxygen and the oxidation of this collector at the surface must be anodic to the equilibrium potential for the thio ion/dithiolate couple. They correlated the rest potential of a range of sulphide minerals in different thio-collector solutions with the products extracted from the surface as shown in Table 1.2 and 1.3. It can be seen from these Tables that only those minerals exhibiting rest potential in excess of the thio ion/disulphide couple formed dithiolate as a major reaction product. Those minerals which had a rest potential below this value formed the metal collector compoimds, except covellite on which dixanthogen was formed even though the measured rest potential was below the reversible potential. Allison et al. (1972) attributed the behavior to the decomposition of cupric xanthate. 

Ever since the mixed potential model has been proposed, the interaction mechanism between thio-collector and sulphide minerals has been usually explained on the basis of this model. The principle of the mixed potential model can be schematically shown in Fig. 4.1. Here, E respectively... 

Although there have been a lot of investigations on the interactions of sulphide minerals with thio-collectors in terms of the mixed potential principle, there are still much controversy about the products formed on a sulphide mineral in the presence of a collector in different conditions. In the following sections, the effects of potential on the flotation and formation of surface products of many kinds of sulphide minerals will be introduced based on the results of flotation, electrochemical measurement, surface analyses and thermodynamic calculations. 

FTIR Analysis of Adsorption of Thio-Collectors on Sulphide Minerals... 

From the point of view of electrochemistry of flotation, a depressant is, however, defined as a reagent by the addition of which the oxidation of the mineral surface occurs at lower potential than collector oxidation or formation of metal collector salt which may be also decomposed imder the conditions given in the discussions which follow. Under these conditions, the mixed potential model becomes one of mineral oxidation and oxygen reduction, the oxidation of the thio collector or the formation of the metal collector is suppressed, and the mineral will remain... 

ZnS is a broad band semiconductor, the electron in the fully occupied valence band is difficult to be excited up to the conduction band. There is less free electron in ZnS, and then it is not easy to accelerate the electrochemistry oxidation of surface. That is to say, the dissolution of ZnS from mineral surface is difficult and has little chance to react with thio-collectors. When substituted by Cu or Fe ions, the forbidden gap of doped ZnS will decrease and the quantity of free electrons in ZnS will increase. This variation will enhance the electrochemistry activity of ZnS. 

The most important raw materials for the production of non-ferrous metals, such as copper, lead, zinc, nickel, cobalt, molybdenum, antimony and cadmium, are the sulfide minerals. The use of collectors containing various thio-type functional groups has proved to be the most successful in the flotation of these minerals. Some of these compounds are shown in Table 1. 

These collectors are effective only under oxidizing conditions, and it is generally accepted that the species that confers hydrophobicity on the mineral surface is either a chemisorbed metal thio compound or the oxidized form of the collector, dithiolate. The amounts of each species formed will depend on the relative stabilities of the metal—sulfur and sulfur—sulfur bonds. The formation of four-membered chelate rings is also possible with soft metal ions such as copper(I) because the largely covalent character of the bond in this instance is able to overcome the strain within the ring by extensive electron delocalization. This could account for the >artial selectivity of some of these reagents for the copper minerals, which has been put to good use in the sequential flotation of copjrer, lead and zinc from complex sulfide ores. ... 

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