Tellurium recovery

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. 

Saturate with hydrogen sulfide and, if necessary, reserve supernate for tellurium recovery (N. B. tellurium as tellurate will not precipitate with hy-... 

Pemoval of Other Impurities. After softening, the impurities that may stiU remain in the lead are silver, gold, copper, tellurium, platinum metals, and bismuth. Whereas concentrations may be tolerable for some lead appHcations, the market values encourage separation and recovery. The Parkes process is used for removing noble metals and any residual copper, and the KroU-Betterton process for debismuthizing. 

Manufacture and Recovery. Electrolytic copper refinery slimes are the principal source of selenium and its sister element, tellurium, atomic numbers 34 and 52, respectively. Electrolytic copper refinery slimes are those constituents in the copper anode which are not solubilized during the refining process and ultimately accumulate in the bottom of the electrorefining tank. These slimes are periodically recovered and processed for their metal values. Slimes generated by the refining of primary copper, copper produced from ores and concentrates, generally contain from 5—25% selenium and 2—10% tellurium. 

Selenium occurs in the slimes as intermetallic compounds such as copper silver selenide [12040-91 -4], CuAgSe disilver selenide [1302-09-6], Ag2Se and Cu2 Se [20405-64-5], where x < 1. The primary purpose of slimes treatment is the recovery of the precious metals gold, silver, platinum, palladium, and rhodium. The recovery of selenium is a secondary concern. Because of the complexity and variabiUty of slimes composition throughout the world, a number of processes have been developed to recover both the precious metals and selenium. More recently, the emphasis has switched to the development of processes which result in early recovery of the higher value precious metals. Selenium and tellurium are released in the later stages. Processes in use at the primary copper refineries are described in detail elsewhere (25—44). 

Purifying Selenium and Tellurium. Selenium recovery processes generally yield a metal product which contains some tellurium, and, correspondingly, recovered tellurium generally contains some small amount of selenium (37,41). 

Like selenium, tellurium minerals, although widely disseminated, do not form ore bodies. Hence, there are no deposits that can be mined for tellurium alone, and there are no formally stated reserves. Large resources however, are present in the base-metal sulfide deposits mined for copper, nickel, gold, silver, and lead, where the recovery of tellurium, like that of selenium, is incidental. 

Fig. 1. Flow sheet for recovery of tellurium from copper slimes.

Anode impurities either dissolve in the electrolyte or fall to the bottom of the electrolytic cell as anode slime. These slimes contain silver, gold, selenium, and tellurium and represent a very significant value. Thus, the recovery of by-products from the anode slime is an important operation. 

Treatment of slimes for economic recovery of silver, gold, selenium, tellurium, and other trace elements requires fusion and oxidation in a furnace. The furnace gases are exhausted through a wet scrubber followed by an ESP to recover the metals. 

Ores in which the gold is in chemical combination in the form of an alloy, typically with tellurium, this is less common, but it creates recovery problems where it does occur. 

Sulfide ores usually contain small amounts of mercury, arsenic, selenium, and tellurium, and these impurities volatilize during the ore treatment. All the volatilized impurities, with the exception of mercury, are collected in the dust recovery systems. On account of its being present in low concentrations, mercury is not removed by such a system and passes out with the exit gases. The problem of mercury contamination is particularly pertinent to zinc plants since the sulfidic ores of zinc contain traces of mercury (20-300 ppm). The mercury traces in zinc sulfide concentrates volatilize during roasting and contaminate the sulfuric acid that is made from the sulfur dioxide produced. If the acid is then used to produce phosphatic fertilizers, this may lead to mercury entering the food chain as a contaminant. Several processes have been developed for the removal of mercury, but these are not yet widely adopted. 

Petit [563] has described a method for the determination of tellurium in seawater at picomolar concentrations. Tellurium (VI) was reduced to tellurium (IV) by boiling in 3 M hydrochloric acid. After preconcentration by coprecipitation with magnesium hydroxide, tellurium was reduced to the hydride by sodium borohydrate at 300 °C for 120 seconds, then 257 °C for 12 seconds. The hydride was then measured by atomic absorption spectroscopy. Recovery was 90 - 95% and the detection limit was 0.5 pmol/1. 

Additional advantages are the possibility of generating the reducing agents in situ as well in catalytic amounts in the presence of an inexpensive co-reductant, and recovery of the tellurium material (for example, elemental tellurium from the above inorganic reagents and ditellurides from tellurols). 

Human exposure has caused headache and dyspnea. Two subjects accidentally exposed to tellurium hexafluoride after leakage of 50g into a small laboratory experienced garlic breath, fatigue, a bluish-black discoloration of the webs of the fingers, and streaks on the neck and face. Complete recovery occurred without treatment. 

Tellurium dioxide in its orthorhombic form occurs in nature as mineral tellurite. It is mined from natural deposits. Also, tellurium dioxide is produced as an intermediate during recovery of tellurium metal from anode shmes of electrolytic copper refining (See Tellurium, Production). The dioxide also is prepared by treating tellurium metal with hot nitric acid to form 2Te02 HNO3. The product then is heated to drive off nitric acid. 

Tellurium. The NIOSH Method S-204 for analysis of in air was originally developed using Te(0H)2 (8). RTI applied this procedure to the analysis of the pure metal. The procedure involves the use of both nitric and perchloric acids during the digestion. Recoveries were excellent, 97 percent. An additional set of samples were subjected to a digestion involving no perchloric acid,... 

Acute oral parenteral tellurium intoxication in animals results in restlessness, tremor, diminished reflexes, paralysis, convulsions, somnolence, coma, and death. Hematuria was prompt and occurred in all animals. Exposure of weanling rats to a diet containing elemental tellurium results in a peripheral neuropathy characterized by segmental demyelination and minimal axonal degeneration. It is noteworthy that functional recovery occurred despite... 

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