Mineral metal-xanthate

Alkali metal xanthates are prepared in high yield from reaction of amyl alcohols with alkah metal hydroxide and carbon disulfide (39—42). The xanthates are useful as collectors in the flotation of minerals and have minor uses in vulcani2ation of mbber and as herbicides (39,41). 

The adsorption of collectors on sulfide mineral occurs by two separate mechanisms chemical and electrochemical. The former results in the presence of chemisorbed metal xanthate (or other thiol collector ion) onto the mineral surface. The latter yields an oxidation product (dixanthogen if collector added is xanthate) that is the hydrophobic species adsorbed onto the mineral surface. The chemisorption mechanism is reported to occur with galena, chalcocite and sphalerite minerals, whereas electrochemical oxidation is reportedly the primary mechanism for pyrite, arsenopyrite, and pyrrhotite minerals. The mineral, chalcopyrite, is an example where both the mechanisms are known to be operative. Besides these mechanisms, the adsorption of collectors can be explained from the point of interfacial energies involved between air, mineral, and solution. 

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... 

According to the mixed potential theory, an anodic reaction can occur only if there is a cathodic reaction proceeding at finite rate at that potential (Rand and Woods, 1984). For the flotation systems, the cathodic reaction is usually given by the reduction of oxygen. The corresponding anodic reaction involves interaction of xanthate on the sulphide minerals in various ways, including the reaction of xanthate with the sulphide mineral (MS) to form metal xanthate and the oxidation of xanthate to dixanthogen (X2) at the mineral surface. 

The mixed potential of the sulphide mineral in the flotation pulp will determine the oxidation product on its surface. If the mixed potential of the mineral in the presence of oxygen, xanthate and other reagents is above the mixed potential for the X7X2 redox couple, then the reaction will produce dixanthogen on the surface. If the mixed potential is lower than the X /Xz redox couple, metal xanthate reaction will take place rendering the surface hydrophobic. 

AEROPHINE 3418A promoter is widely used ia North and South America, AustraHa, Europe, and Asia for the recovery of copper, lead, and ziac sulfide minerals (see Elotatton). Advantages ia comparison to other collectors (15) are said to be improved selectivity and recoveries ia the treatment of complex ores, higher recoveries of associated precious metals, and a stable grade—recovery relationship which is particularly important to the efficient operation of automated circuits. Additionally, AEROPHINE 3418A is stable and, unlike xanthates (qv), does not form hazardous decomposition products such as carbon disulfide. It is also available blended with other collectors to enhance performance characteristics. 

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. 

Abstract In this chapter, the depression mechanism of five kinds of depressants is introduced respectively. The principle of depression by hydroxyl ion and hydrosulphide is explained which regulates the pH to make the given mineral float or not. And so the critical pH for certain minerals is determined. Thereafter, the depression by cyanide and hydrogen peroxide is narrated respectively which are that for cyanide the formation of metal cyanide complex results in depression of minerals while for hydrogen peroxide the decomposition of xanthate salts gives rise to the inhibitation of flotation. Lastly, the depression by the thio-organic such as polyhydroxyl and poly carboxylic xanthate is accounted for in detail including die flotation behavior, effect of pulp potential, adsorption mechanism and structure-property relation. 

Miner. Process Extra. Metall. Rev., 2 203 - 234 Hayes, R. A. and Ralston, J., 1988. The collectorless flotation and separation of sulphide minerals by control. Inter. J. Miner. Process, 23 55 - 84 Hepel, T. and Pomianowski, A., 1977. Diagrams of electrochemical equilibria of the system copper-potassium ethyl xanthate-water at 25°C. Int. J. Miner. Process, 4 345 - 361 Heyes, G. W. and Trahar, W. J., 1977. The natural floatability of chalcopyrite. Int. J. Miner. Process, 4 317-344... 

Woods, R., 1996. Chemisorption of thiols on metal and metal sulphide. In J. O M Bockris, B. E. Conway, R. E. White (eds.). Modem Aspects of Electrochemistry. 29 401 - 453 Woods, R., Young, C. A., Yoon, R. H., 1990. Ethyl xanthate chemisorption isotherms andEh-pH diagrams for the copper/water/xanthate and chalcocite/water/xanthate systems. Inter. J. Miner. Process, 30 17 - 33... 

Depressants (or deactivators) are chemicals that ensure that undesired particles remain hydrophilic and therefore do not get floated. Conversely to the activation of zinc sulfide by copper ions above, zinc ions from zinc sulfate act as a depressant for zinc sulfide. Another example is the use of cyanide to complex with copper and prevent adsorption of collectors in the flotation of base-metal sulfides with xanthates. There are many other depressants but they tend to be quite specific to one of a few types of minerals. In some cases, such as some uses of cyanide as a depressant, the mechanism of depressant action remains unclear. 

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. 

Promoters or collectors provide the substances to be separated with a water-repellent air-avid coating that will adhere to air bubbles. Typical collectors for flotation of metallic sulfides and native metals are dithiophosphates and xanthates. Fatty acids and their soaps, petroleum sulfonates, and sulfonated fatty acids are widely used as collectors in flotation of fluorspar, iron ore, phosphate rock, and others. Fuel oil and kerosene are used as collectors for coal, graphite, sulfur, and molybdenite. Cationic collectors such as fatty amines and amine salts are widely used for separation of quartz, potash, and silicate minerals. 

Rao, S.R. and Finch.. T.A.. Base metal oxide flotation using long chain xanthates. Int. J. Miner. Process., 69. 251. 2003. 

A significant development in this regard was the correlation of the solubility products of a series of heavy metal-ethyl xanthate salts with the floatability of corresponding sulfide minerals by (Kakovsky, 1980). He found the decrease in the order of the solubility product of sulfide minerals to be in line with the increase in the order of their floatability. From exchange reactions of lead-diethyl xanthate, the well-known Barsky equation can be derived ... 

Using Eq. (4.42), the pMe -pH diagrams given in Fig. 4.40 can be generated. In this diagram, the horizontal line at the bottom represents the minimum concentration of metallic ions which is necessary for the formation of ethyl xanthate salt the intersection point of horizontal and vertical lines gives the upper pH limit for the mineral flotation. 

Solubility products of collector-metallic ion compounds (see Appendix C) suggest that the sulfide mineral collectors such as xanthates, mercaptans and thiophosphates containing sulfur bonding atom in the minerophilic group can form compounds of low solubility products with ions of elements with affinity for copper(II). They can not form insoluble... 

Collectors for nonsulfide minerals containing O atom, such as fatty acids and sulfonates, react with various metallic ions by ionic bond, and they have high solubility in water. The solubility becomes low only when the hydrocarbon chains in the molecules are long. In contrast, collectors for sulfide minerals, such as xanthates possessing only a short chain, the S bonding atom reacts with metallic ions to form covalent bonds with lower polarity. 

This includes reactions of the polymer groups with metallic sites on the particle surface that may result in the formation of stable or insoluble compounds through covalent, ionic or coordination bonding. Carboxyl flocculants such as polyacrylic acid and carboxyl-methyl cellulose can chemisorb on the surface of calcite and sphalerite which have calcium or zinc sites on them. Certain flocculants, such as cellulose and starch with xanthate and polyacrylamide with dithiocarbamate with high chemically active groups, have been found to exhibit selective reaction with sulfide minerals. Such complexing polymers have been investigated for their use in selective flocculation processes. 

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