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By W. E. Mitchell

ELECTROLYTIC, production of cadmium at the Great Falls plant started in the first part of the year 1925. Prior to that time, an experi¬mental unit had been in operation for a few months during the year . 1922. At present the plant is the largest producer of cadmium, not only in the United States but in the world. Electrolytic cadmium is characterized by its very low content of impurities. The main impurities, which are lead, copper, zinc, and iron, do not aggregate more than 0.05 per cent., leaving a cadmium content better than 99.95 per cent. The consumption of cadmium has increased rapidly since the war, with the growing use in the plating industry. Cadmium plating has come into prominence because of its connection with the automobile and radio industries. As a protective coating, a deposit of, cadmium is superior to zinc. Cadmium is also used extensively in alloys. Important among these is the alloy with copper used in telephone and trolley wire. In proportion of 0.5 to 1.2 per cent., cadmium adds materially to the strength and wearing qualities. Practically all commercial zinc concentrates contain a small amount of cadmium. In the electrolytic zinc process, the cadmium that is dissolved in the regular leaching operation is removed from solution with metallic zinc, generally added in the form of zinc dust. This precipitate also contains the copper taken into solution and the excess of zinc dust, which is required in order to insure a complete removal of all impurities. The precipitate is treated by a separate process to recover the copper, cadmium and excess zinc. In order to make the metals more soluble and to render insoluble such impurities as iron, arsenic and antimony, the precipitate is roasted. The roasting is carried out in gas-fired McDougall furnaces, with a roasting temperature of about 700° C.

Jan 1, 1930

As the Mount Morgan electrolytic chlorine plant is the first of its kind installed in Australia, and as the details of this method of producing chlorine have, up to the present time, been kept more or less secret all over the world, the author trusts that this paper may fill a gap in the technical literature of the subject.When an electric current is passed through a strong solution of sodium chloride the following reaction takes place -2 NaCl + 2 H 20 = 2 NaOH + C1 2 + H 2 Chlorine gas is liberated at the anode or entering pole of the current, while caustic soda and hydrogen are formed at the cathode or leaving pole of the current. If the two electrodes be simply immersed in a vessel containing salt and the current be turned on, there will be no result save slight smell of escaping chlorine gas. The passage of the current will have certainly split up the salt water according to the above equation, but as the products would be in juxtaposition they would immediately reunite, and the electrical energy would have been spent without any beneficial result having been obtained. Therefore, the all-important problem in designing an electrolytic chlorine cell is the finding of some effective means of isolating from each other the chlorine and caustic: soda as soon as liberated from the...

Jan 1, 1911

By W. K. Tolley

The U.S. Bureau of Mines (USBM) is currently investigating the electrochemistry of mineral flotation. A significant need in this area is greater reliability of sensors. The USBM is testing electrolytic methods to clean and condition redox-sensing electrodes to improve the reliability and extend the service life of these instruments in the harsh physical and chemical environment of mineral processing slurries. A novel method for removing scale from fouled electrodes has been developed that includes anodic polarization to 1.2 V versus the Ag/AgCl reference potential, followed by brief potentiodynamic conditioning. Laboratory results show that this technique removes calcarious deposits from gold sensing electrodes and returns the electrode to useful service within approximately 10 min. Mechanical abrasion to remove the scale is thereby avoided.

Jan 1, 1994

By Jackson Jenkins

The second survey of world copper SXEW plants has been completed. Solvent extraction and electrowinning data published in 1996 has been updated and leach data from seventeen plants is now included. The following pages list the results of the thirty- two plants that responded to the survey. Selected information is summarized in graphical form.

Jan 1, 1999

By W. G. Davenport

A survey of world copper refining tankhouse .practices has been carried out. This paper compiles the results and examines changes in operating practices .since the similar 1987, 1991 and 1995 surveys. Continuing trends are the installation of ISA Process and Kidd Process stainless steel cathode technology, polymer concrete cells, anode preparation machines and automatic cranes. Instrumentation and automatic control are increasing, particularly for addition agent optimization; solvent extraction .and ion exchange techniques are being increasingly applied for electrolyte purification. The overall consequences of these changes have been 'improved cathode purities and enhanced tankhouse productivities.

Jan 1, 1999

By M. Moats

World copper refining tankhouse practices have been surveyed. This survey is a supplement to previous surveys that have been carried out in the 1987, 1991, 1995, 1999, 2001 and 2003. On a world basis, process technology trends include the further installation of automated electrode handling systems including permanent cathode systems, automatic anode preparation and cathode handling machines, section switches, fully automatic cranes and polymer concrete cells. General plant process control has increased with more automation of material handling in the copper refining tankhouse. The general trend for most greenfield copper refining projects remains in eastern Asia.

Jan 1, 2007

By John H. Schloen

"The object of this paper is to review electrolytic copper refining as it was in 1954(1), as it is now in 1984, and to comment on the many improvements which have been made in the last thirty years.In 1954, and even in 1984, the ASTM specification B 115 for cathode copper was 99.90% minimum copper plus silver content and 100% minimum electrical conductivity, IACS standard. However, to meet competition and to satisfy the requirements of the fabricators and the electrical industry, the electrolytic refinery must supply a product of 99.95% to 99.96% minimum copper content, and 101fJlo minimum electrical conductivity.The range of cathode impurities reported by 20 major copper refineries in 1954 are given in Table I.The much more rigid British Specification, DD 78, for high-purity cathode copper, specifies individual elements, as well as groups of elements, as shown in Table 2.The Svenska test has been replaced by a similar procedure which uses 2.r mm diameter wire. The ISO test is the one listed in the DD 78 specification. In Table 3, corresponding values for the Svenska and ISO test s are given for various wire bar coppers."

Jan 1, 1986

By John H. Schloen

Copper refineries are constantly looking for methods to upgrade their plants to reduce refining costs and to improve the purity of their electrolytic cathodes at the same time that the purity of the anodes they refine is being lowered by the rehabilitation of reverberatory furnace smelters to one of the direct smelting processes. The comments given below are based on the answers to the questionnaire returned bf the 36 copper refineries that represent 66% of the western world s refining capacity. Eleven refineries employ some form of uniform weight anade casting, e.g., Outokumpu, Contilanode, Mitsubishi, Lurgi, or Hazelett. This type of anode casting presents the best possibility for improving cathode purity. The cathode press of Phelps Dadge can improve current efficiencies and cathode quality. The press is used on first-run cathodes, after 48-60 hours, on half-cells at a time without interruption of the cell current. One refinery interrupts current for sever.al hours to allow the anode slime to settle before the, cathode pressing. The cathode press is now used at eight refineries. Apart from periodic reverse current (PRC), it is not expected that current densities will be increased. Thirty refineries, using direct current, average 231 amps/M, with a low of 178 and a high of 350. Five refineries use PRC at an average of 338 amps/M, with a low of 290 and a high of 380. Current efficiencies are good at an average of 94%, with a low of 88% and a high of 99% for the 34 refineries that reported. It must be remembered that the cycle efficiency with PRC is about 93%., so that the effective current efficiency with PRC would be only .94 X .93 or 87% However, PRC should be considered seriously for refinery expansions because it can save about 25% on capital costs.

Jan 1, 1987

By David Kellogg

THE electrodeposition of iron has been practiced for many years. The earlier work along this line was directed toward the preparation of pure metal, but later applications were the production of thin adherent coatings as used in the electrotyping of Russian banknotes in 1860. A historical discussion of this subject, however, would require too much space and would be inconclusive. Much has been written on the subject but no two experimenters use the same methods or materials. During the war, the British army repair, shops developed a method for building up worn parts of automotive machinery, aero engines, etc., using the cold surfate . bath and low-current density method.1 The method has been used successfully in commercial work for the production of about 6000 repaired parts, therefore experiments along the same lines have since been made at the Westinghouse research laboratory. The apparatus used was essentially that described in the article mentioned except that the current -used for cleaning was obtained from a 3/4-kw. 60-volt, house-lighting generator, direct connected to a 2-h.p., 870-r.p.m., 440-volt, three-phase, type CS induction motor; while the plating current was taken from the storage batteries at any desired voltage. The anodes were made from 0.036 in. (0.9 mm.) Armco iron made into cylinders 5 in. (127 mm.) long by 8 in. (203 mm.) in diameter with a disk of 1/8 -in. (3.17 mm.) micarta, having a 2 in. hole in the center fitted at each end of the cylinder for stirring. The anodes were hung on a wooden rocker frame driven by a wooden connecting I rod directly connected to a small reducing gear, such as is sold by most of the apparatus supply firms; 3 gal. stoneware crocks were used as containers. The solution used by Thomas, 75 gm. of the crystallized ferrous ammonium sulfate per liter, was tried, using the current density recommended by him; namely, 0.33 amp. per sq. dm. Under these conditions the deposit on a ½ -in.

Jan 2, 1922

By Basant L. Tiwari

An electrolytic process, based on a three-layer concentration cell, to extract magnesium from commercial aluminum alloy scrap has been examined. The process was repeatedly tested at 1025 K with two cells of d1fferent sizes, 0.6 kg and 5 kg feed aluminum, to have a better understanding of the opera ting parameters and evaluate the scale-up potential. In both cells, the magnesium content of the scrap was selectively reduced ?from 1. 1 to less than 0.1 wt.% at anodic current dens-Hy as high as 1. 1 A/cm2 with current efficiency exceeding 85%. Magnesium was recovered in the form of salt coated globules. Comparison of performances for the two cells suggests that the process can be scaled up. With further development, this process could become a viable alternative for demagging secondary aluminum.

Jan 1, 1985

The electrochemical dissolution of gold and other noble metals in hydrochloric acid using alternating current has been investigated. The experimental results show that this technique is efficient for dissolving pure noble metals and offers prospects for their extraction from wastes and poor ores.

Jan 1, 1992

Develop technology for preparing thick corrosion-resistant coatings and electroforms of iron-chromium-nickel alloys. Approach To reduce the United States' dependence upon foreign sources for supplies of strategic and critical metals such as chromium, cobalt, and nickel, new technology must be devised to conserve these valuable commodities. One approach being investigated by the Bureau of Mines is the use of a modified-aqueous-electrodeposition method to prepare thick (-25 µm), complex alloy coatings (e.g., stainless steel composition) with properties similar to the commercial alloys. An alloy coating on a low-alloy steel or carbon steel substrate would require significantly less strategic and critical metals than those contained in an equivalent mass of the commercial alloy. Coatings applied to appropriate mandrel materials make possible the preparation of intricately-shaped alloy electroforms (near-net-shape parts). As a result, the loss of valuable metals associated with machining finished products would be minimized.

Jan 1, 1986

By Robert Pike

THE first authentic description of an iron bath for the deposition of iron is probably that of Bottger in 1846, who used a bath containing ferrous sulfate and ammonium chloride. In 1861, Kramer deposited iron from ferrous chloride solution. Electrolytic iron was produced in 1.869 by Bietz, who used it for making some magnetic tests. In the same year, Klein is said to have worked out his process. Jacobi1 in 1869 described the results obtained in electroplating with iron on copper for making dies and plates for bank notes, by Klein's process. A letter from Klein to Jacobi describes the bath more fully. It consisted of FeSO4 + (NH4)2S04. Lenz2 described ?some properties of electrolytically precipitated iron. He used Klein's bath, FeSO4 + MgSO4 + MgCO3, to neutralize and obtained fine-grained and hard iron. His conclusions were as follows: 1. Electrolytic iron and copper contain gases, notably hydrogen. 2. The volume of gas absorbed by iron varies within wide limits, but it is easy for iron to take up very considerable quantities of gas. 3. The absorption of gas is principally in the first formed layers of iron. 4. When iron is heated, gas begins to come off below 100°, principally hydrogen. 5. Heated to redness, reduced iron oxidizes in water, in part at least at the expense of the oxygen of the water, decomposing it and setting free hydrogen, which is partly or wholly absorbed. Siemens,3 in 1889, was the first to propose a general process embodying a step for leaching a sulfide mineral with ferric chloride or sulfate and a step for regenerating the leach and depositing iron on a cathode in a diaphragm cell. So far as is known, Siemens did not carry out his patent

Jan 1, 1930

By Carlos A. Aranda

The Smelting and Refining Department of Cerro de Pasco Corporation is located at La Oroya at an altitude of 3,720 meters (12,205 feet) in the Peruvian Andes. Producing lead, zinc and copper as well as twelve by-product metals and chemicals, the smelter is among the world's most complex. With the intake of high-bismuth ores in 1934, electrolytic lead refining by a modified Betts process was piloted and the plant went into commercial production in 1937 at a nominal capacity of 100 M.T. per day. After expansions in 1950 and 1963, nominal capacity has increased to 250 M.T. per day. Anodes spaced at 10.8 cm centre to centre and starting sheets are both set into the cells by overhead cranes. The asphalt-lined concrete cells are arranged in a Walker side-by-side configuration, and the electrolyte, circulating at 13 l/min./cell, is a solution of locally-produced hydrofluosilicic acid and lead fluosilicate. The corrosion cycle is limited to four days due to high impurity content of the bullion, which has successfully been treated at contents of up to 9% impurities. The cathodes are melted, drossed, and cast into blocks and pigs assaying 99.997 + % lead. The anodes with the blanket of slime adhering, are washed with electrolyte and condensate makeup water to remove the concentrated lead fluosilicate entrapped in the slimes. The slimes are then removed with high-pressure water sprays, centrifuged and sent to another plant for recovery of silver, gold, bismuth, selenium, tellurium, and antimony.

Jan 1, 1970

By R. S. Dean

IN THE COURSE of its investigations directed toward providing strategic metals from domestic sources and toward utilizing power from Federal power projects in West, the Bureau of Mines concluded some years ago that the development of a method for producing electrolytic manganese might well be an important step towards both goals. Accordingly, laboratory investigations were undertaken in 1935. Further studied on a relatively large laboratory scale indicated that electrolytic manganese could be made from domestic ores at a cost not out of line with other nonferrous metals. On the basis of these results, the Electro Manganese Corp. Operating under U.S. Patent 2,119,560 issued to S, M, Shelton and assigned to the Secretary of the Interior for administration, undertook commercial production of electrolytic manganese at Knoxville, Tenn, This company has brought the process through the pilot-plant stage successfully, and is now regularly producing approximately one ton a day.

Jan 1, 1941

To devise an economical, environmentally acceptable method for recycling scrap lead-acid batteries. Approach A combination electrorefining-electrowinning method for recycling lead metal and sludge from scrap batteries was devised which produces a 99.99 + percent pure lead product and eliminates the lead and sulfur oxide emissions that are the normal by-products of high-temperature smelting processes. How the Method Works Lead metal grids and lugs are separated from the battery sludge by washing and screening, and are melted and cast into anodes for electrorefining by the Betts process. The electrolyte used is fluosilicic acid, a large volume waste product generated during the production of phosphate fertilizer. During the electrorefining process, impurities in the anode are trapped and held in an adherent slime blanket on the surface as the anode dissolves while pure metallic lead is deposited on a lead cathode. The major problem in the past has been to recover the lead from the battery sludge which consists of approximately 60 percent lead sulfate, 21 percent lead, and 19 per-cent lead dioxide. In the flow sheet developed by the Bureau

Jan 1, 1983

By B. J. Scheiner

Electrooxidation of cinnabar mercury ores (HgS) was investigated as a means of providing an effective and economical hydrometallurgical technique for extraction of mercury from its ores, particularly those too low in grade to allow economical metal recovery by retorting or furnacing techniques. Oxidation was accomplished by electrolysis of ere slurried with brine. Cinnabar was dissolved by oxidation of the insoluble sulfide to soluble mercuric salts. The mercury ion in a brine solution forms a stable tetrachloro complex. Typical laboratory experiments required I to 7 hours of electrolysis at 35-percent pulp density in a brine solution that contained 4 to 20 weight-percent sodium chloride (NaCl). Power consumption ranged from 10 to 50 kwhr/ton of dry ore. Mercury extraction values between 90 and 99 percent were obtained with all of the ores investigated. Subsequent mercury recovery from leach solutions was readily accomplished by precipitation on zinc. Pilot mill experiments in a 100- to 200-lb/hr extraction plant are in progress to quantify power and reagent requirements, and extraction and recovery data obtained to date closely parallel those obtained in the laboratory.

Jan 1, 1970

By T. H. Aldrich

(San Francisco Meeting, October, 1911.) THERE are two conditions generally prevailing upon the earth-those within atmospheric influence, tending towards oxidation, and those away from atmospheric influence, tending towards reduction. Practically all mineral substances from mines of any depth are in a reducing condition. Since the cyanide process, in order to dissolve silver or gold, requires that the prevailing conditions under which it operates shall be oxidizing, and the materials usually acted upon being of a reducing character, it becomes necessary to supply oxygen to the solution carrying the cyanide. This oxygen is usually supplied through the medium of dissolved air in the solution, or through the medium of various chemical compounds, which upon combining with the solution or the ore give off a part of their oxygen. Strange as it may seem, practically all mineral substances are partly soluble in water, especially water carrying alkali or cyanide. The greater the surface exposed and the finer the material is ground, the greater will be the rate of dissolving of the reducing agents from the ore into the cyanide solution. In most cases, if the solution carrying the ore particles is agitated with air, the air will dissolve into the solution faster than will the reducing-agents; but in some cases the reducing-agents will dissolve more rapidly on account of easy solubility or greater surface exposed. It is a dissolving race between the oxygen from the air and the reducing-agents from the ore, and if the reducing-agents predominate, cyanide will not dissolve the gold from the ore. In many cases it will dissolve some of the gold, because in a mass of irregular shape some of the gold particles might be exposed upon the outside surface of a particle of rock;' but if the solution had to penetrate through cracks, the side-walls of which were lined with reducing-agent-

Feb 1, 1912

By Met B. E

During the operation of the Parkes process of desilverising, and in the earlier days of the continuous process, gold and silver were removed separately from softened lead bullion. Gold was removed in the Parkes process by a selective zincing, and -in the continuous process by treatment with zinc in a special de-golding kettle, in each case a crust being obtained carrying the gold and a small portion of the silver. Actually the process could have been more correctly termed a de-copperising process, on accountof the relatively large amount of this metal present, and its affinity for zinc, which caused it to enter the crusts produced.The crust was treated in reverberatory furnaces, where the bulk of the copper and zinc was removed in by-products, and the resulting "gold bullion" cupelled to give adore bullion containing approximately 2,000 ounces gold per ton.For the purpose of parting this dore, a small Balbach-Thum plant of 11 cells was used, and once each six months a short campaign was conducted on the accumulated metal.With the development of the process of de-copperising smelter bullion by means of sulphur, when a bullion averaging about .004% copper was constantly available for refining, the need for a separate de-golding process disappeared.The de-golding kettle of the Continuous Process...

Jan 1, 1937

By G. Van Weert, A. van Sandwijk, O. W. J. S. Rutten

"Cathodic and anodic reactions in an acidic nitrate medium were studied in reference to the production of electrolytic manganese dioxide from pyrolusite' (Mn02) ores by reductive leaching. Two USA ores were investigated. The reductant for the pyrolusite ore is produced cathodically in an electrolytic cell and can either be nitrous acid (HN02) or nitric oxide gas (NO). In this work emphasis was placed on the nitrous acid leach. In a high-temperature leach in a nitrous/nitric acid medium, manganese and silver are solubilized and iron is not. Anodic electrowinning of manganese dioxide from the acidic manganese nitrate electrolyte yields flaky y-Mn02, similar to that produced from sulfate and chloride electrolytes. Cathodic regeneration of nitrorts acid was studied in a membrane cell in 1.0 M nitric acid and 0.0 to 0.1 M nitrous acid on a' platinized titanium cathode. At cathode potentials ranging from +950 to +700 mV (SHE), cathodic reduction to nitrous acid takes place, at cathode potentials < +700 mV, cathodic reduction of nitrous acid to nitric oxide takes place. A conceptual process is presented and discussed.IntroductionManganiferous-silver oresLarge reserves of manganiferous-silver ores are present in the Southwestern United States and Latin America. These ores are generally refractory to hydrometallurgical methods of treatment, due to the insolubility of the higher oxides of manganese (Mn 4+) in all common lixiviants such as cyanide solutions, dilute sulfuric acid, nitric acid, ammonia, salt solution, thiosulfates, etc. The silver is either bound by the insoluble manganese, or is rendered inaccessible to cyanide leach solution by the surrounding manganese mineralization.Higher oxides of manganese will dissolve if they are first reduced pyrometallurgically to manganous oxide (Mn2+). This is a widely used pretreatment for manganese dioxide ores and subsequent dissolution in sulfuric acid is common. In order to avoid the pyrometallurgical pretreatment with its large energy requirements and gaseous emissions, fully hydrometallurgical processes have been proposed. These processes are based on the presence of a reductant in solution, in order to reduce the insoluble higher oxides of manganese to soluble lower oxides. Aqueous S02 has been proposed and tested on industrial scale by the U.S. Bureau of Mines. After washing, silver could be extracted by cyanidation. The neutralization of the pulp prior to cyanidation however causes problems in filtration and the reagent consumptions are high [1]. More recently, acidified thiourea and bacteria were proposed for the solubilization of both manganese and silver in a single leach step. High extractions were obtained, but drawbacks of these methods are high reagent consumption or slow kinetics [2,3]. For the options of manganese recovery from the leach filtrate, precipitation with persulfate or ammonium carbonate and ion exchange have been proposed. The proposed options for silver reclaim are precipitation with either zinc or Na2S and adsorption onto activated carbon."

Jan 1, 1997