Sulfide minerals

Fig. 1. Effect of particle size on the flotation recovery of a sulfide mineral. Mineral chalcocite [2112-20-9J, CU2S reagent potassium ethyl xanthate,...

Electrochemical processes at some sulfide mineral surfaces lead to the formation of oxidation products as in the case of the hydrophobization of... 

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. 

The rate of dissolution is limited by oxygen availabiUty rather than by cyanide concentration. When oxygen solubiUty is reduced by water salinity or by consumption by ore constituents such as sulfide minerals, enrichment of the air with oxygen or addition of hydrogen or calcium peroxide improves leaching kinetics and decreases cyanide consumption (10). 

Bacterial leaching is another example of oxidizing dissolution whereby specific bacteria either directiy attack the sulfide mineral or indirectiy enhance the regeneration of the oxidant. 

Nickel [7440-02-0] Ni, recognized as an element as early as 1754 (1), was not isolated until 1820 (2). It was mined from arsenic sulfide mineral deposits (3) and first used in an alloy called German Silver (4). Soon after, nickel was used as an anode in solutions of nickel sulfate [7786-81 A] NiSO, and nickel chloride [7718-54-9] NiCl, to electroplate jewelry. Nickel carbonyl [13463-39-3] Ni(C02)4, was discovered in 1890 (see Carbonyls). This material, distilled as a hquid, decomposes into carbon monoxide and pure nickel powder, a method used in nickel refining (5) (see Nickel and nickel alloys). 

Ocean Basins. Known consohdated mineral deposits in the deep ocean basins are limited to high cobalt metalliferous oxide cmsts precipitated from seawater and hydrothermal deposits of sulfide minerals which are being formed in the vicinity of ocean plate boundaries. Technology for drilling at depth in the seabeds is not advanced, and most deposits identified have been sampled only within a few centimeters of the surface. 

Flotation Reagents. Only one sulfide mineral flotation collector is manufactured from phosphine, ie, the sodium salt of bis(2-methylpropyl)phosphinodithioic acid [13360-78-6]. It is available commercially from Cytec Industries Inc. as a 50% aqueous solution and is sold as AEROPHINE 3418A promoter. The compound is synthesized by reaction of 2-methyl-1-propene [115-11-7] with phosphine to form an iatermediate dialkylphosphine which is subsequently treated with elemental sulfur [7704-34-9] and sodium hydroxide [1310-73-2] to form the final product (14). The reactions described ia equations 10 and 11... 

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. 

Leaded Zinc Oxide. Oxides containing more than 5 wt % basic lead sulfate are classified as leaded and are made ia the American process from high lead materials, usually lead sulfide mineral, or by blending ziac oxide and basic lead sulfate. There is only one manufacturer ia the United States and the product contains 20—28 wt % basic lead sulfate. Leaded oxides are used only ia mbber ia the United States. 

Montana. These deposits consist of stibnite and other sulfide minerals containing base metals and silver or gold. Ores of the complex deposits are mined primarily for lead, copper, 2inc, or precious metals antimony is a by-product of the treatment of these ores. 

Microbiological leaching of copper and uranium has been commercially developed and research has iadicated that microorganisms may be used to oxidize complex antimony sulfide minerals (22,23). If this technology is developed commercially, it may aHow for the exploitation of many low grade antimony deposits. 

Cadmium occurs primarily as sulfide minerals ia ziac, lead—ziac, and copper—lead—ziac ores. Beneftciation of these minerals, usually by flotation (qv) or heavy-media separation, yields concentrates which are then processed for the recovery of the contained metal values. Cadmium follows the ziac with which it is so closely associated (see Zinc and zinc alloys see also Copper Lead). 

Flotation. The slurry of ground ore leaving the grinding circuit may be separated from part of the water in thickeners or may go directly to the flotation cells. The latter are rectangular tanks into which air is injected or drawn via impellers. Flotation is based on producing a water-repellent chemical film on the exposed sulfide minerals in the ground ore. The sulfide minerals collect on the surface of the air bubbles and rise to the top of the flotation cell, where they can be removed from the froth. The froth overflows the cells in collector troughs called launders. 

Preparation of the Media Various sohd materials have been used to prepare the media. In the initial development of the process, a suspension of sand and also mixtures of barite and clay were used for separating coal from slate. Galena (lead sulfide mineral) was also used... 

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. 

Indium (0.24 ppm) is similar in abundance to Sb and Cd, whereas T1 (0.7 ppm) is close to Tm and somewhat less abundant than Mo, W and Tb (1.2 ppm). Both elements are chalcophiles (p. 648), indium tending to associate with the similarly sized Zn in its sulfide minerals whilst the larger T1 tends to replace Pb in galena, PbS. Thallium(I) has a similar radius to Rb and so also concentrates with this element in the late magmatic potassium minerals such as feldspars and micas. 

Figure 15.1 Position of the chalcophilic elements in the periodic table these elements (particularly those in white) tend to occur in nature as sulfide minerals the tendency is much less pronounced for the elements in normal black type.

The third major source of sulfur is pyrite and related sulfide minerals. The ore is roasted to secure SO2 gas which is then usually used directly for the manufacture of H2SO4 (p. 708). Again air pollution by vS02 gas emissions has been the subject of increasing legislation and control during the past three decades (p. 698). 

The modem process uses a potassium-sulfate-promoted vanadium(V) oxide catalyst on a silica or kie,selguhr support. The SO2 is obtained either by burning pure sulfur or by roasting sulfide minerals (p. 651) notably iron pyrite, or ores of Cu, Ni and Zn during the production of these metals. On a worldwide basis about 65% of the SO2 comes from the burning of sulfur and some 35% by the roasting of sulfide ores but in some countries (e.g, the UK) over 95% conies from the former. 

Sulfide minerals and K. Sulfides are among the least soluble ionic compounds. Their AQ, values are often smaller than 10-25. For this reason, many sulfides are found as minerals, for example (clockwise from the left), iron pyrite (FeS2), yellow orpiment (AS2S3). and black galena (PbS). 

Claisse40 has made a comprehensive attack on mineral analysis. He realized that fusion to give a glass disk could be used at once to remove Class II deviations. (7.8) and to give samples in which a (Equation 6-6) varies very little from one sample to another. Accordingly, he developed the fusion of minerals (other than sulfide minerals) with fluxes based on borax (100 mg of sample to 10 grams of borax) when graphite or sulfides are present, oxidation must precede the borax fusion. Internal standards or materials intended to fix the value of a may be added before... 

Iron, Fe, the most widely used of all the d-metals, is the most abundant element on Earth and the second most abundant metal in the Earth s crust (after aluminum). Its principal ores are the oxides hematite, Fe203, and magnetite, Fc C)4. The sulfide mineral pyrite, FeS2 (see Fig. 15.11), is widely available, but it is not used in steelmaking because the sulfur is difficult to remove. 

Copper, Cu, is unreactive enough for some to be found as the metal, but most is produced from its sulfides, particularly the ore cbalcopyrite, CuFeS2 (Fig. 16.10). The crushed and ground ore is separated from excess rock by froth flotation, a process that depends on the ability of sulfide ores to be wetted by oils but not by water. In this process, the powdered ore is combined with oil, water, and detergents (Fig. 16.1 l). Then air is blown through the mixture the oil-coated sulfide mineral floats to the surface with the froth, and the unwanted copper-poor residue, which is called gangue, sinks to the bottom. 

The magnetic criterion is particularly valuable because it provides a basis for differentiating sharply between essentially ionic and essentially electron-pair bonds Experimental data have as yet been obtained for only a few of the interesting compounds, but these indicate that oxides and fluorides of most metals are ionic. Electron-pair bonds are formed by most of the transition elements with sulfur, selenium, tellurium, phosphorus, arsenic and antimony, as in the sulfide minerals (pyrite, molybdenite, skutterudite, etc.). The halogens other than fluorine form electron-pair bonds with metals of the palladium and platinum groups and sometimes, but not always, with iron-group metals. 

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