Selenium leaching

Figure 5. Amount of total selenium leached from the ferrite crystals formed from Se(IV) or Se(VI) soln.

Wet Process. The sodium arsenate and stannate slag are treated by a leach and precipitation process to produce calcium arsenate, calcium stannate, and a sodium hydroxide solution for recycle. The sodium antimonate filtercake containing selenium, tellurium, and indium is treated in a special metals refinery to recover indium and tellurium. 

There are areas (22) where selenium levels in the soil are very low these include regions of volcanic activity like that adjacent to the Cascade mountains in the Pacific Northwest states of the United States and the central north island of New Zealand. There, because the heat of emption volatilized the selenium, the residual soil parent material is virtually devoid of selenium. Other areas of low soil-selenium reflect leaching of selenium out of the top soil, as in the Canterbury plain on New Zealand s south island. Areas of selenium deficiency have negative implications for animal and human health. 

The roasted pellets or extmdes are ground and leached in water. The hexavalent selenium dissolves as sodium selenate [13410-01 -0] Na2Se04. Sodium teUurate, being highly insoluble in the now very strongly alkaline solution, remains in the residue. The separation between selenium and tellurium is readily achieved, provided all tellurium is oxidized to the hexavalent state. 

Selenium has also been shown to act synergistically with bismuth to improve the machinabifity of brasses (113). The machining properties are similar to those of the leaded brasses used in plumbing appfications. Environmental concerns arising from the leaching of lead brasses necessitates a replacement of the lead. 

In mineral technology, sulfur dioxide and sulfites are used as flotation depressants for sulfide ores. In electrowinning of copper from leach solutions from ores containing iron, sulfur dioxide prereduces ferric to ferrous ions to improve current efficiency and copper cathode quaHty. Sulfur dioxide also initiates precipitation of metallic selenium from selenous acid, a by-product of copper metallurgy (326). 

Most commercial tellurium is recovered from electrolytic copper refinery slimes (8—16). The tellurium content of slimes can range from a trace up to 10% (see Seleniumand selenium compounds). Most of the original processes developed for the recovery of metals of value from slimes resulted in tellurium being the last and least important metal produced. In recent years, many refineries have changed their slimes treatment processes for faster recovery of precious metals (17,18). The new processes have in common the need to remove the copper in slimes by autoclave leaching to low levels (<1%). In addition, this autoclave pretreatment dissolves a large amount of the tellurium, and the separation of the tellurium and copper from the solution which then follows places tellurium recovery at the beginning of the slimes treatment process. 

Tellurium is stUl recovered in some copper refineries by the smelting of slimes and the subsequent leaching of soda slags which contain both selenium and tellurium. The caustic slags are leached in water and, using the controlled neutralization process, tellurium is recovered as tellurium dioxide. 

Production and Economic Aspects. Thallium is obtained commercially as a by-product in the roasting of zinc, copper, and lead ores. The thallium is collected in the flue dust in the form of oxide or sulfate with other by-product metals, eg, cadmium, indium, germanium, selenium, and tellurium. The thallium content of the flue dust is low and further enrichment steps are required. If the thallium compounds present are soluble, ie, as oxides or sulfates, direct leaching with water or dilute acid separates them from the other insoluble metals. Otherwise, the thallium compound is solubilized with oxidizing roasts, by sulfatization, or by treatment with alkaU. The thallium precipitates from these solutions as thaUium(I) chloride [7791 -12-0]. Electrolysis of the thaUium(I) sulfate [7446-18-6] solution affords thallium metal in high purity (5,6). The sulfate solution must be acidified with sulfuric acid to avoid cathodic separation of zinc and anodic deposition of thaUium(III) oxide [1314-32-5]. The metal deposited on the cathode is removed, kneaded into lumps, and dried. It is then compressed into blocks, melted under hydrogen, and cast into sticks. 

Zinc (76ppm of the earth s crust) is about as abundant as rubidium (78 ppm) and slightly more abundant than copper (68 ppm). Cadmium (0.16 ppm) is similar to antimony (0.2 ppm) it is twice as abundant as mercury (0.08 ppm), which is itself as abundant as silver (0.08 ppm) and close to selenium (0.05 ppm). These elements are chalcophiles (p. 648) and so, in the reducing atmosphere prevailing when the earth s crust solidified, they separated out in the sulfide phase, and their most important ores are therefore sulfides. Subsequently, as rocks were weathered, zinc was leached out to be precipitated as carbonate, silicate or phosphate. 

In the lower fan areas Se concentrations were monitored up to 400 pg/L. Similar historical distribution of soil Se content and shallow groundwater content indicate that dissolved selenium species were leached from saline soils by irrigation water. The drainage discharge of shallow groundwater and subsurface irrigation water was accompanied by increasing accumulation of Se in Kesterson Reservoir. 

Pesticide wastes that are hazardous by reason of the characteristics are those which are either solvent based and have a flash point <60 °C are aqueous and have a pH <2.0 or >12.5 release HCN or H2S upon contact with acids or leach greater than threshold levels of one or more of the elements arsenic, barium, cadmium, chromium, lead, mercury, selenium and silver, or the pesticides endrin, lindane, methoxychlor, toxa-phene, 2,4-D or 2,4,5-TP. To date, these are the only pesticides for which thresholds have been established. 

Alternatively, raw anode slimes are aerated with hot dilute sulfuric acid to remove copper. Slimes are then mixed thoroughly with sodium carbonate and roasted in the presence of sufficient air. Sodium selenate formed is leached with water. Hydrochloric acid is added to this selenate solution. Treatment with sulfur dioxide precipitates elemental selenium. Alternatively, the selenate solution is evaporated to dryness. Sodium selenate is reduced to sodium selenide by heating with carbon at high temperatures. Sodium selenide is leached with water. Air is blown over the solution. Selenide is oxidized to elemental selenium which precipitates. 

Grisafe, D. A., Angino, E. E. Smith, S. M. 1988. Leaching characteristics of a high-calcium fly ash as a function of pH a potential source of selenium toxicity. Applied Geochemistry, 3, 601-608. 

Cementation, the process by which a metal is reduced from solution by the dissolution of a less-noble metal, has been used for centuries as a means for extraction of metals from solution, and is probably the oldest of the hydrometallurgical processes. It is also known by other terms such as metal displacement or contract reduction, and is widely used in the recovery of metals such as silver, gold, selenium, cadmium, copper and thallium from solution and the purification of solutions such as those used in the electrowinning of zinc. The electrochemical basis for these reactions has been well established414 and, as in leaching reactions, comprises the anodic dissolution of the less-noble metal coupled to the cathodic reduction of the more-noble metal on the surface of the corroding metals. Therefore, in the well-known and commercially exploited44 cementation of copper from sulfate solution by metallic iron, the reactions are... 

Selenium. Selenium has been determined colorimetrically by formatrion of a diaminobenzidine complex, 420 nm, after an oxidation and distillation (13). Method S-190 for selenium in air extracts the analyte from filters by 0.1 N nitric acid leaching. The nitric acid extracts are aspirated into an argon/hydrogen-air flame, and the absorbance is recorded for the 196 nm analytical line. The method discourages the use of a carbonaceous flame like air-acetyelene. Many analysts use air acetylene because it is convenient. Background correction is required for either flame type. 

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