Copper slime

Soda. Ash Roasting. Some of the first processes to recover selenium on a commercial basis were based on roasting of copper slimes with soda ash to convert both selenium and tellurium to the +6 oxidation state. Eigure 1 shows flow sheets for two such processes. Slimes are intensively mixed with sodium carbonate, a binder such as bentonite, and water to form a stiff paste. The paste is extmded or peUetized and allowed to dry. Care in the preparation of the extmdates or pellets is required to ensure that they have sufficient porosity to allow adequate access to the air required for oxidation. 

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

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. 

Selenium is distributed widely in nature and is found in most rocks and soils at concentrations between 0.1 and 2.0 ppm (Fishbein 1983). However, elemental selenium is seldom found naturally, but it is obtained primarily as a byproduct of copper refining (Fishbein 1983). Selenium is contained in the constituents of the copper anode that are not solubilized during the copper refining process and ultimately accumulate on the bottom of the electrorefining tank. These constituents, usually referred to as slimes, contain roughly 5-25% selenium and 2-10% tellurium. Selenium is commercially produced by either soda ash roasting or sulfuric acid roasting of the copper slimes. 

Sulfuric Acid Roasting. In this method, the copper slimes are mixed with sulfuric acid and roasted at 500-600 °C to produce selenium dioxide, which volatilizes readily at the roasting temperature. The selenium dioxide is reduced to elemental selenium during the scrubbing process with sulfur dioxide and water. The resultant commercial grade selenium can be purified to 99.5-99.7% (Hoffmann and King 1997). 

In both the sulfuric and nitric acid processes, the dorn metal must be in shot form prior to treatment to secure a reasonably rapid reaction. A number of steps also may be required in processing the dorne metal to remove miscellaneous impurities, particularly in treating material from copper-anode slime (31). 

Metals less noble than copper, such as iron, nickel, and lead, dissolve from the anode. The lead precipitates as lead sulfate in the slimes. Other impurities such as arsenic, antimony, and bismuth remain partiy as insoluble compounds in the slimes and partiy as soluble complexes in the electrolyte. Precious metals, such as gold and silver, remain as metals in the anode slimes. The bulk of the slimes consist of particles of copper falling from the anode, and insoluble sulfides, selenides, or teUurides. These slimes are processed further for the recovery of the various constituents. Metals less noble than copper do not deposit but accumulate in solution. This requires periodic purification of the electrolyte to remove nickel sulfate, arsenic, and other impurities. 

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). 

Miscellaneous. Where a copper refinery is adjacent to a lead (qv) plant it is feasible to recover the selenium in slimes by smelting them in conjunction with lead-bearing materials. Utilizing the lower temperatures needed to melt lead, the selenium is volatilized from a lead bath or cupel blown with air. The selenium is recovered from flue dust and fume by scmbbing. This is the process used by Union Miniere at its Hoboken plant in Belgium. 

Fujimura and A. Katai, Selenium Recovery from Copper Electrolysis Slimes at Mitsubishi Osaka Refinery, paper no. 82-12, TMS, Warrendale, Pa. 

J. E. Hoffmann, "Recovery of Selenium from Electrolytic Copper Refinery Slimes," in V. Kudryk, D. A. Corrigan, and W. W. Liang, eds.. Precious Metals Mining Extraction and Processing H, TMS, Warrendale, Pa., 1983. 

D. H. Jennings, R. T. McAndrew, and E. S. Stratigakos, A Hydrometallurgical Methodfor Recovering Selenium and Tellurium from Copper Refinery Slimes, paper no. A 68-69, TMS, Warrendale, Pa., 1968. 

R. K. Manahan and F. Loewen, "Treatment of Anode Slimes at the INCO Copper Refinery," paper presented at CIMMeeting, Halifax, Nova Scotia, 1972. 

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. 

J. H. Schloen and E. M. Elkin, Trans. ATME 188, 764 (1950) A. Butts, ed.. Treatment of Electrolytic Copper Eefmery Slimes, Reinhold Publishing Corp., New York, 1954, Chapt. 11. 

L. A. Soshrukova and M. M. Kupchenko, Pererahotka Mednelektrolitnykh Shlamov ([Treatment of Copper Electrolysis Slimes), Metallurgiya, Moscow, 1978. 

The washed slime is dried and melted to produce slag and metal. The slag is usually purified by selective reduction and smelted to produce antimonial lead. The metal is treated ia the molten state by selective oxidation for the removal of arsenic, antimony, and some of the lead. It is then transferred to a cupel furnace, where the oxidation is continued until only the silver—gold alloy (dorn) remains. The bismuth-rich cupel slags are cmshed, mixed with a small amount of sulfur, and reduced with carbon to a copper matte and impure bismuth metal the latter is transferred to the bismuth refining plant. 

When the ore contains a large amount of clay minerals, these form difficult to separate slimes, which hinder the recovery of the minerals (see Clays). The tailing from the scavenger cells can be cycloned to remove the slimes before the coarse material is floated in a tailings retreatment plant. The flotation product from the rougher cells of this plant can be reground and cleaned. This additional treatment of the tailings from the main copper flotation plant may improve the recovery of metal values by 1—3%. 

The series system was used in the past as an alternative to the multiple system. In this system only anodes were charged and a potential was maintained between the ends of each cell so that copper dissolved from one anode was plated on the adjacent anode. After a sufficient period of time, all the original anode copper was replaced by a cathodic deposit and the impurities were either in the form of anode slime or in solution. The series system demanded highly uniform anodes, a requirement that was difficult to meet with horizontal equipment. 

The precipitated copper from this reaction is an important constituent of the slime that collects at the bottom of the electrolytic cells. The accumulation of copper as well as of impurities such as nickel, arsenic, antimony, and bismuth is controlled by periodic bleed-off and treatment in the electrolyte purification section. 

By-Product Recovery. The anode slime contains gold, silver, platinum, palladium, selenium, and teUurium. The sulfur, selenium, and teUurium in the slimes combine with copper and sUver to give precipitates (30). Some arsenic, antimony, and bismuth can also enter the slime, depending on the concentrations in the electrolyte. Other elements that may precipitate in the electrolytic ceUs are lead and tin, which form lead sulfate and Sn(0H)2S04. 

The mud or slime is coUected from the bottom of the electrolytic ceUs and pumped to the sUver refinery, where it is processed for recovery of copper, precious metals, selenium, and, in many cases, teUurium. The anode slime contains 2—20% selenium as copper and sUver selenides, whereas gold exists as the metal and in combination with teUurium. A flow diagram is shown in Figure 8. 

In general, the slime components are separated in sUver refineries by employing combined pyrometaUurgical and hydrometaUurgical methods. In the first step copper is removed from the slimes in an autoclave using sulfuric acid and oxygen. The reaction is shown in equation 34. 

The major part of this blister copper is further purified electro lytic ally by casting into anodes which are suspended in acidified CUSO4 solution along with cathodes of purified copper sheet. As electrolysis proceeds the pure copper is deposited on the cathodes while impurities collect below the anodes as anode slime which is a valuable source of Ag, Au and other precious metals. 

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