Anode impurities

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. 

Refining operations have two principal wastestreams, waste electrolyte and cathode and anode washwater. Spent electrolyte is normally recycled. A bleed stream is treated to reduce copper and impurity concentration. Varying degrees of treatment are necessary because of the differences in the anode copper. Anode impurities, including nickel, arsenic, and traces of antimony and bismuth, may be present in the effluent if the spent electrolyte bleed stream is discharged. Tables 3.14 and 3.15 present classical and toxic pollutant data for raw wastewater in this subcategory. 

The principal anode impurities which can reduce aluminum purity are iron, silicon, titanium, vanadium and manganese. 

Electrorefining — Electrolytic process aimed at the purification of a metal (M). Impure metal anodes are elec-trochemically dissolved in a suitable electrolyte (solution of a M salt) to form ions of the desired element, which are reduced at the cathodes, effecting a selective deposition of M with high purity. Depending on its nature, the anode impurities are left as anodic slimes (collected from the bottom of the electrolytic cell) or as ions in the electrolyte (continuously bled to a purification circuit). This performance can be easily understood by noting that the elements with higher reduction potential than M will not undergo oxidation and thus are re-... 

The insoluble anode impurities are collected as anode slimes from the bottom of the cells and from washing the scrap anodes. The slimes are treated in a precious metals plant for recovery of gold, silver, and other valuable by-products. In conventional slime treatment, the first step is usually the decopperizing in an autoclave at high temperatures and pressures in sulfuric acid media. The filtrate contains tellurium and chlorides. Tellurium is removed by copper, after which the filtrate returns to electrolysis. 

Soto, H.J. 2005. The effect of ammonia as an anode impurity on the performance of PEM fuel cells. PhD disser. University of South Carolina, Columbia. 

Siher(Il) oxide, AgO, is a black solid, Ag Ag 02, obtained by anodic or persulphate oxidation of an AgNOs solution. Continued anodic oxidation gives impure Ag203. Argentates, e.g. K.AgO, containing silver(I) are known. 

Crude lead contains traces of a number of metals. The desilvering of lead is considered later under silver (Chapter 14). Other metallic impurities are removed by remelting under controlled conditions when arsenic and antimony form a scum of lead(II) arsenate and antimonate on the surface while copper forms an infusible alloy which also takes up any sulphur, and also appears on the surface. The removal of bismuth, a valuable by-product, from lead is accomplished by making the crude lead the anode in an electrolytic bath consisting of a solution of lead in fluorosilicic acid. Gelatin is added so that a smooth coherent deposit of lead is obtained on the pure lead cathode when the current is passed. The impurities here (i.e. all other metals) form a sludge in the electrolytic bath and are not deposited on the cathode. 

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). 

Decopperized blast furnace bulHon is softened to reduce impurities below 2% before casting as anodes. The electrolyte is a solution of lead fluosUicate [25808-74-6] PhSiF, and free fluosUicic acid [16961 -83-4]. Cathode starting sheets are made from pure electrolytic lead. The concrete electrolytic ceUs are lined with asphalt or a plastic material such as polyethylene. 

Electrorefining. Electrolytic refining is a purification process in which an impure metal anode is dissolved electrochemicaHy in a solution of a salt of the metal to be refined, and then recovered as a pure cathodic deposit. Electrorefining is a more efficient purification process than other chemical methods because of its selectivity. In particular, for metals such as copper, silver, gold, and lead, which exhibit Htfle irreversibHity, the operating electrode potential is close to the reversible potential, and a sharp separation can be accompHshed, both at the anode where more noble metals do not dissolve and at the cathode where more active metals do not deposit. 

Impure copper is cast in the shape of anodes - 0.9 by 1.0 m and 3.5—4.5-cm thick, weighing 300—400 kg. These anodes are cast with lugs that... 

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. 

The electrorefining of many metals can be carried out using molten salt electrolytes, but these processes are usually expensive and have found Httie commercial use in spite of possible technical advantages. The only appHcation on an industrial scale is the electrorefining of aluminum by the three-layer process. The density of the molten salt electrolyte is adjusted so that a pure molten aluminum cathode floats on the electrolyte, which in turn floats on the impure anode consisting of a molten copper—aluminum alloy. The process is used to manufacture high purity aluminum. 

Piebaked anodes aie produced by molding petroleum coke and coal tar pitch binder into blocks typically 70 cm x 125 cm x 50 cm, and baking to 1000—1200°C. Petroleum coke is used because of its low impurity (ash) content. The more noble impurities, such as iron and siUcon, deposit in the aluminum whereas less noble ones such as calcium and magnesium, accumulate as fluorides in the bath. Coal-based coke could be used, but extensive and expensive prepurification would be required. Steel stubs seated in the anode using cast iron support the anodes (via anode rods) in the electrolyte and conduct electric current into the anodes (Fig. 3). Electrical resistivity of prebaked anodes ranges from 5-6 Hm anode current density ranges from 0.65 to 1.3 A/crn. ... 

Molten aluminum is removed from the cells by siphoning, generally daily, into a cmcible. Normally the metal is 99.6—99.9% pure. The principal impurities are Ee, Si, Ti, V, and Mn, and come largely from the anode, but also from the alumina. 

Atmospheric corrosion is electrochemical ia nature and depends on the flow of current between anodic and cathodic areas. The resulting attack is generally localized to particular features of the metallurgical stmcture. Features that contribute to differences ia potential iaclude the iatermetaUic particles and the electrode potentials of the matrix. The electrode potentials of some soHd solutions and iatermetaUic particles are shown ia Table 26. Iron and sUicon impurities ia commercially pure aluminum form iatermetaUic coastitueat particles that are cathodic to alumiaum. Because the oxide film over these coastitueats may be weak, they can promote electrochemical attack of the surrounding aluminum matrix. The superior resistance to corrosion of high purity aluminum is attributed to the small number of these constituents. 

Flaws in the anodic oxide film are usually the primary source of electronic conduction. These flaws are either stmctural or chemical in nature. The stmctural flaws include thermal crystalline oxide, nitrides, carbides, inclusion of foreign phases, and oxide recrystaUi2ed by an appHed electric field. The roughness of the tantalum surface affects the electronic conduction and should be classified as a stmctural flaw (58) the correlation between electronic conduction and roughness, however, was not observed (59). Chemical impurities arise from metals alloyed with the tantalum, inclusions in the oxide of material from the formation electrolyte, and impurities on the surface of the tantalum substrate that are incorporated in the oxide during formation. 

The formation of anodic and cathodic sites, necessary to produce corrosion, can occur for any of a number of reasons impurities in the metal, localized stresses, metal grain size or composition differences, discontinuities on the surface, and differences in the local environment (eg, temperature, oxygen, or salt concentration). When these local differences are not large and the anodic and cathodic sites can shift from place to place on the metal surface, corrosion is uniform. With uniform corrosion, fouling is usually a more serious problem than equipment failure. 

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