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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 A. W. Bryson

Electrolytic precipitation of ammonium diuranate by A. W. BRYSON. Ph.D. (Member) Continuous precipitation of ammonium diuranate from a solution of uranyl sulphate and ammonium sulphate in the cathode compartment of an electrolytic cell has been investigated. It is found that the rate of precipitation and the settling rate of the precipitate can be correlated with the current consumed per unit volume of catholyte solution. The weight fraction of uranium in the dried solid product appears to be constant over the range of operating conditions used.

Jan 9, 1975

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

By M. Rockandel

"Universal Dynamics Ltd. of Vancouver, Canada has developed, patented and commercialized the ""REMERC"" process for the treatment of mercury contaminated sludges and soils. Mercury is extracted into an acidified and oxidizing, sodium chloride brine solution. REMERC was initially developed to treat mercury contaminated EPA listed wastes (K106) generated by the chlor-alkali industry. More recent work has expanded the capability;' of REMERC to include remediation of mercury contaminated sites, equipment and building materials.In the process mercury is currently recovered from solution by cementation on iron powder in an agitated reactor. The process recovers high purity elemental mercury (99.9% purity). Cementation typically recovers about 90-95% of the mercury in 30 minutes. Higher recovery is not necessary because of the recirculation of the leach solution. When treating highly contaminated chloralkali wastes (5-13% mercury content), REMERC will reduce the mercury laden solutions from 400-1,000 mg/L mercury to 50-100 mg/L. In the treatment of less concentrated wastes «1,000 mg/kg mercury) such as those encountered in site remediation, the treated solutions will generally contain 10-20 mg/L mercury. Cementation while being simple and able to achieve the required recovery has the. undesirable properties of; requiring a solid-liquid separation and adding iron to solution which must be precipitated, ultimately increasing the weight of residue to landfill. .The potential advantages of electrolysis were recognized early in the development of REMERC. Mercury electrolysis is well known in gold and chloralkali processing. Initial testwork utilized a liquid mercury cathode and a coated titanium anode both common to chloralkali producers. The mercury cathode appeared susceptible to polarization and solution impurities significantly affected performance. Agitation of the mercury pool improved performance but it was still not possible to achieve the reduction objectives. Current efficiencies were low, near 10%, and it was apparent that a relatively large cathode pool would be required to limit the current density. A number of electrode combinations with and without a membrane were then tested in a vertical electrode' configuration but the desired performance was not obtained."

Jan 1, 1997

By Yves Pépin, Sylvain Lefebvre, Dimitrios Filippou, Guillaume Hudon

"Titanium dioxide pigment plants using the so-called “chloride process” produce considerable amounts of chloride waste, which contains predominantly iron chloride. In most cases, this waste is dissolved in a weak hydrochloric acid solution and then neutralised. The metal content of the waste is dumped as hydroxide sludge, while its chloride content is lost in an effluent.Rio Tinto Iron & Titanium has developed a new proprietary process whereby pure metallic iron and chlorine gas are recovered from chloride waste by electrolysis. This process uses a two compartment cell separated by an anion exchange membrane to prevent iron cycling between its trivalent and divalent valence. The cathode is made of titanium Grade 7, while the anode is a dimensionally stable one of the type “metal–mixed metal oxide” (MMO) for the evolution of chlorine gas. The catholyte is concentrated and pH-adjusted iron-rich chloride solution originating from chloride waste. The anolyte is recirculating solution containing alkali or alkali earth chlorides such as MgCl2, NaCl, etc. Current efficiencies above 90% can be achieved at temperatures about 80°C using catholyte solutions almost saturated in iron chloride and other chlorides.In this paper, we discuss the details of this process, and how this could be integrated within a chloride pigment plant for the treatment of chloride wastes."

Jan 1, 2016

"Hematite pellets were electro-deoxidized to iron in molten sodium hydroxide to produce iron containing about 10-wt % oxygen. The anodic reaction was the evolution of oxygen on an inert nickel anode. Before the electrochemical reaction, there is a reaction between sodium hydroxide and ferric oxide to form sodium ferrite and, in order to compensate for the reduction in sodium oxide content, 1 wt % sodium oxide is added to the melt. In a laboratory cell, the cell voltage was 1.7 V with a current density of 5000 A m-2, a current efficiency of 90% and an energy consumption of 2.8 kWh kg-1.Introduction The iron and steel industry contributes about 2.3 bn tonnes/annum of the carbon dioxide to the atmosphere, which is about 10% of the total, and some believe that, in order to prevent a catastrophic rise in the earth’s temperature, carbon dioxide emissions must be reduced by 50% come 2050. However, by 2050, it is likely that the iron and steel industry would have grown significantly so that the production may have risen to 2 or 3 bn tonnes/year so in order to meet the 50 % reduction on today’s figure, the carbon dioxide may have to be reduced to 25% or less, which is a very demanding requirement. There are probably three ways of reducing the carbon dioxide output:1. By capture and sequestration, but this may be technically very demanding.2. Reduction using hydrogen in place of carbon."

Jan 1, 2009

By X Hu, J Björkvall, L Sundqvist Ökvist

The metal production industry is a significant contributor to global CO2 emissions due to the use of fossil fuels such as coal and coke. To mitigate these emissions and meet climate goals, innovative and sustainable technologies are required. Molten salt electrolysis is a promising technology that directly produces metals from their precursor sulfides or oxides using electricity. When combined with renewable electricity and an inert anode, the electrolysis process can be carbon neutral. This paper presents the results of two pilot-scale studies on the electrolytic reduction of metal oxides and sulfides in molten salts. The first study focuses on the electrolytic reduction of chalcopyrite in molten NaCl-KCl salt. The results demonstrate that in situ separation of copper, iron, and sulfur is possible, enabling the extraction of all valuable elements without CO2 emissions. Furthermore, the findings underscore the capability to eliminate impurities like zinc, antimony, arsenic, and mercury from the electrolysis product. The second study investigates the electrolytic reduction of pure/synthetic chemicals of wüstite, hematite, and magnetite, as well as a magnetite-type iron ore in molten NaOH salt. The findings reveal a stepwise reduction of iron oxides from high valence to low valence, ultimately leading to the production of metallic iron electrolytically. Notably, this study underscores the challenges associated with the selection of an economically viable and durable inert anode material for efficient oxygen generation. These results indicate that molten salt electrolysis provides a sustainable and green route for base metal production. The use of this technology has the potential to significantly reduce CO2 emissions in the metal production industry, contributing to achieving climate goals.

Jun 19, 2024

By A. D. Burns, K. M. Nikolaisen

Electrolytic reduction followed by the addition of sulfuric acid and the application of heat can be used to selectively crystallize uranous sulfate from solution. This approach, when coupled with downstream thermal decomposition, forms the basis of a process for primary uranium recovery and purification where much of the sulfuric acid value can be recovered and recycled. In this process, a purified uranium (VI) leach solution is first electrolytically reduced to uranium (IV) in a membrane electrolysis cell. Sulfuric acid is then added to the solution which, in conjunction with the input of heat, causes the crystallization of uranous sulfate tetrahydrate. The precipitate is then dried and thermally decomposed to U3O8, which releases a mixture of high-purity SO2, SO3, oxygen, and water vapour. This gas can be recovered as sulfuric acid in an existing acid plant, processed through a new wet sulfuric acid process, or absorbed directly into the upstream electrolyte as a substitute for fresh acid in the crystallization step. This process has been shown to be practical, efficient, and cost-effective on the laboratory scale, and could be practiced on the industrial scale using commercially available equipment. This paper focuses on the thermal decomposition process and options for acid recovery.

Jan 1, 2020

By EDWARD B. DURHAH

(San Francisco Meeting, UCtober, 1911.) THE refinery at the San Francisco Mint takes the bullion purchased by the receiving department, and carrying more than 200 parts of precious metals in 1000, or, in mint parlance; over 200 fine, and separates and refines the various metals contained therein, using electrolytic processes exclusively. Bullion containing silver is treated in cells charged with a nitric electrolyte. These cells produce fine silver and leave a residue rich in gold. The residue from the silver-cells, together with crude gold-bullion, is treated in cells having a chloride electrolyte. These produce fine gold and leave a residue containing silver chloride. The latter is reduced to the metallic state with zinc and is then treated in the silver-cells. The various waste solutions and the wash-waters, after being freed from the bulk of their precious metals, still contain copper and other metals. These are removed by scrap-iron, and are then treated in the copper-cells, having a sulphate electrolyte. These cells produce pure copper, and collect a residue containing lead, some gold and silver, and all the metals of the platinum group that were in the bullion. This residue is relatively small, and is melted into bars and stored until sufficient accumulates to warrant treating it for platinum, etc. The refinery occupies three large and three small rooms. The large ones are, a melting-room, 30 by 34 ft.; a cell-room, 39 by 46 ft.; and a wash-room, 30 by 33 ft. The small rooms are used as foreman&apos;s office, laboratory, and generator-room, respectively. The methods here described are those in use in December, 1909, when notes for the present paper were taken.

Oct 1, 1911

SOME notes on the works of the Electrolytic Refining and Smelting Company of Australia will no doubt be of interest to members of the Institute, more especially as much of the work is new to Australasia. As many of the members who may read this paper have not been in a position to visit works of this kind, and are consequently not thoroughly acquainted with all the operations carried on, the author has taken the liberty, in some cases, to enter into explanation which would otherwise be unnecessary. The works are situated at Port Kembla (New South Wales), about fifty miles south of Sydney, and are approachable both by rail and water. The Government has recently built a low-level jetty upwards of five hundred feet long, and intends installing at an early date an electrically operated portable crane to facilitate the handling of material to and from the boats. This will mean: a considerable reduction in the length of time that boats are laid up at the jetty. There are also under construction two breakwaters, which, when complete, will materially assist shipping operation...

Jan 1, 1910