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By R. Woods

INTRODUCTION Gaudin (1), considered that "the mechanism of mineral collection is the central problem of flotation theory". From their work on adsorption phenomena in flotation for more than fifty years (2), Gaudin and his co-workers have made major contributions to the elucidation of this mechanism, a fact acknowledged by their contemporaries in the field (e.g. (3)). Their investigations in a number of areas, e. g. demonstrating that submonolayer quantities of adsorbed collector species can induce flotation, or identifying the influence of substances which can activate or depress (1), have helped to provide the basis for and the development of a theory to account for the interaction between mineral and collector. It was established in the late fifties (4) that the presence of oxygen is a prerequisite for the flotation of metal sulfides with thiol collectors. This fact rendered inadequate the concept of simple ion adsorption being responsible for rendering these minerals hydrophobic. The requirement for oxygen has been explained (1) in terms of this species being a component in chemical reactions between the sulfide surface and the collector. Gaudin has been instrumental in identifying the products of chemical reactions at sulfide minerals (1, 5), a line of work which has been continued particularly by Finkelstein and co-workers in South Africa (6). In presenting a detailed mechanism of the mineral-collector- oxygen interaction, it has often been considered that the mineral surface [must] first be oxidized to a metal oxy-sulfur species which

Jan 1, 1976

By K. A. Kiselev, V. I. Zelentsov, V. P. Nebera

INTRODUCTION Most works on flotation of ions and precipitates from solutions have been summarized recently (1-3). Flotation is more desirable than thickening or centrifuging because of higher recovery, productivity, simplicity of apparatus and better economics in general. Electrolytic flotation that utilizes gases is more favorable than other flotation processes because of the following: higher dispersity of gas bubbles, low coalescence of the bubbles, possibility of gradual regulation of the dispersity and other parameters of flotation (4-5). Flotation from solutions is mostly based on the use of alkaline reagents as precipitants (5). Flotation from acid solutions is less common. We used multicomponent solutions with more than 2-3 components, unlike previous research methods. Acidic flotation allows recirculation of solutions to previous operations such as leaching, etc. REAGENTS FOR PRECIPITATION Electroflotation was studied over a wide range of pH with the addition of ferrocyanide, oxyquinoline, hydroxide and carbonate precipitants. In recent works (1,2,6,7) on flotation of Ni, Cu, Zn from alkaline solutions, mostly ferrocyanides were applied. Our choice was oxyquinoline because of the following: 8-oxyquinoline is a nonspecific reagent for many metals, it is readily soluble in acids and alkalis, oxyquinolates of the studied metals are in soluble compounds, the reagent works over a wide range of pH, it is widely available, oxyquinolate precipitates are stable when exposed to air, are readily floatable, and are easily converted to oxides of the metals by sintering.

Jan 1, 1980

By S. W. Ihle, L. J. Warren

A sample of garnet from the scheelite ore body on King Island, Tasmania, Australia, was upgraded and ground to produce an ultrafine portion suitable for micro-electrophoresis. X-ray and chemical analysis identified the garnet as andradite with some admixed grossular. At neutral pH the garnet particles were negatively charged, their zeta potential becoming rapidly more negative with increasing pH. An iso-electric point was found at pH 3.5. The effects on the zeta-potential of various electrolytes, hydrolyzable metal ions, and flotation collectors were also studied.

Jan 1, 1976

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

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 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

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 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'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

By R. P. E. Hermsdorf

THE electrolytic refining of metals for the removal of undesirable impurities has become a recognized necessity in the nonferrous field. Copper, lead, zinc, nickel, silver and gold have been produced in this manner for years. The United States Metals Refining Co., realizing that considerable quantities of lead and tin could be made available to the trade if a satisfactory method of purification of these metals could be established, decided to investigate the possibilities of electrolytic solder. In cooperation with Dr. Edward F. Kern, of the School of Mines at Columbia University, the company developed a process of electrolytic refining of lead-tin alloys using a tin-lead fluosilicate electrolyte. A pilot plant was installed in November, 1927, and the commercial unit was put in October, 1929. Since that time thousands of tons of electrolytic solder have been produced in this plant and consumed by all branches of industry that use solder.

Jan 1, 1936

By C. A. Hansen

INTRODUCTION It has been the experience of the writer, during some. five years' work with electrolytic zinc, that the zinc cell is perhaps more- sensitive to impurities in the electrolyte than the analytical methods as yet developed for the chemical identification and determination of these impurities; but that, when proper purification methods have been applied to a given solution, the behavior of the cell is quite independent of the original sources from which the zinc sulphate has been derived. It has also appeared that the behavior of the zinc cell is the best and surest check on the correctness and thoroughness of the purification methods used, because it indicates the presence of both current impurities. and cumulative impurities derived from the leaching of the ore; it also in

Jan 3, 1918

By C. A. Hansen

ROASTING FERRUGINOUS ZINC-SULFIDE ORES IN 1912, Mr. J. B. Ideating was developing an electrolytic-zinc process for application to the ores of the Bully Hill mines of the General Electric Co. These ores consist of blende and pyrite so finely crystallized and so intimately mixed that no mechanical separation of the individual minerals had been found possible. The ore was reduced to about 60 mesh and roasted in a hand-rabbled reverberatory furnace preparatory to leaching with sulfuric acid. The extractions obtained were quite irregular, varying from a minimum of about 70 per cent. to a maximum of about 90 per cent. This irregularity led to the construction of a small electrically heated roasting furnace, and to the study of roasting under definitely controllable conditions. From time to time, these studies have been extended to other ores. Several commercial-plant operators profess to have gained useful information from the results of these studies and it is hoped that their usefulness may be extended by this publication. EXPERIMENTAL ELECTRIC ROASTING FURNACE The furnace used for experimental work is shown in Fig. 1. One fire-clay sagger, or pot, was set within another and the space between the two filled with Silox heat insulation. The hearth is a cast-iron plate with an imbedded ribbon of nichrome wire; this wire heater is connected to a potential regulator, which permits a very close voltage control. A mechanically driven arm is fitted with rabble blades so arranged that a uniformly thick ore bed may be maintained indefinitely. This arm is usually driven at about one revolution per minute but its speed of rotation can be varied as desired. Compressed air is led into the furnace through a meter, and it was found necessary to preheat the air in order to secure the definitely isothermal conditions sought.

Jan 8, 1919

C. A. HANSEN (communicated appendix*).-Since the above paper was written, tests have been conducted with a view to securing a sounder basis for discussing the effects of temperature on the behavior of the zinc cell. The following data, while making no pretense to great accuracy, are still reasonably close. Cells were operated with the same feed solutions, but at varying temperatures, the latter being controlled by means of immersed steam coils. Current efficiencies obtained indicate that the corrosion rate

Jan 11, 1918

By U. C. Tainton

The paper reviews the evolution of electrolytic zinc, describing some of the major obstacles that have been encountered and overcome. The chief remaining limitations of present-day standard practice are: Difficulty of obtaining high extractions, especially from low-grade and complex ores; filtration troubles, if ores contain much soluble silica; and irregularities in electrolysis, if more than certain limited amounts of antimony, arsenic, cobalt; etc., are present in the ores. These factors dictate a relatively high-grade plant feed, thus subjecting the electroytic-zinc process to the same kind of limitations as the zinc smelter. The "high acid process," in which both acid strength and current density are raised to about four times the usual figures, is described. This system concentrates both plant and operations, allows a simple type of flow sheet, and. minimizes some of the difficulties above mentioned. The large-scale operation of the process is described. SOME time ago, at a meeting of the Institute Prof. J. W. Richards1 said, "I take exception to the statement that all the factors in the production of electrolytic zinc were known long ago. There is possible in my opinion an improvement of perhaps 50 per cent. in the new electrolytic processes." An examination of the literature of the subject will show the justness of Professor Richards' contention. The work of the earlier investigators was carried on in the shadow of difficulties that, today, are hardly more than memories. We seldom hear now of zinc sponge, that bête noir of the electrolytic-zinc pioneers. Zinc sponge, was the name given to a peculiar, soft, black, non-adherent form of zinc deposit that was utterly useless for melting into ingot form. At the big plant at Cockle Creek, New South Wales, in 1897, Edgar Ashcroft2 said that the solution in the plant would suddenly, and without ascertainable cause, go "bad" and begin to deposit spongy zinc. The most delicate, even spectroscopic, methods of analysis were unable to detect any difference between "good solution and "bad" solution; either form might change to the other on being kept for a while. When it is added that an outbreak of this insidious disease (which. appeared to

Jan 2, 1924

By George Steintveit

Det Norske Zinkicompani A/S was established in 1924, on the initiative of the Compagnie Royale Asturienne des Mines. Experimental electrothermic zinc production was carried out on industrial scale for a two-year period, but the problems of electrothermic smelting were not solved. A license for the electrolytic zinc production process was then obtained from the Anaconda Copper Mining Co. A plant for electrolytic zinc production was built, near the small fjord town of Odda in Hardanger, West Norway, The production was based on zinc ore from Spain, and cheap local hydro-electric power. The plant came into operation in 1929. Annual capacity, 36,000 tons. In 1964 a long-term agreement was concluded with Boliden AB by which Det Norske Zinkkompani is secured the raw materials basis for an expansion of the annual capacity to 100,000 tons of zinc, Since World War II, the company has been pursuing extensive research and development programs. As a result, various sections have been rebuilt: nev unloading and storage facilities, a 250 ton per day Fluid Bed Roaster with contact plant, new continuous leaching system, integrating the Jarosite Residue Process, new solution purification section - upgrading the solution quality for a 600 Amp/m2 current density Tank Room operation -, installation of induction furnaces for cathode melting with casting machines and automatic stacking of slabs. Simultaneously, instrumentation, and methods of automatic control have been developed and introduced, providing conditions for optimal plant operations.

Jan 1, 1970

By O. H. Banes

The electrolytic zinc plant of the American Zinc Company located at Sauget, Illinois started operations in April 1941. The plant had a designed capacity of 45(T) per day. The original flow sheet was quite simple, incorporating the low density process. Through the years the capacity of the plant has been increased to the current design of 214(T) cathodes per day. This paper describes the current operation along with typical metallurgical data.

Jan 1, 1970

By Frederick Laist

ABOUT six years ago the Anaconda Copper Mining Co. decided to investigate the possibility of extracting zinc from the ores of certain mines in the Butte district. These ores are of a complex character and contain so much iron and lead that the concentrate contains only 33 to 35 per cent. zinc. Investigations showed that while a high-grade concentrate could not be obtained by ordinary methods, such as tabling and magnetic treatment, a fair grade could be made by the Horwood process. In this method, the concentrate resulting from the flotation of all of the sulfides is given a light roast and this calcine is subjected to flotation in the presence of a large amount of sulfuric acid; the resulting concentrate contains most of the zinc and a residue contains most of the iron. The fact that the lead, copper, and silver are divided approximately equally between the zinc concentrate and the iron residue and the large consumption of acid, which ranged from 50 to 100 lb. (22 to 45 kg.) per ton of concentrates, were serious objections to this plan. The zinc recovery, moreover, was low, as a considerable percentage invariably accompanied the iron. While a profit might be made on the ores by the use of this process, it was thought that other and more promising methods might be devised. After carefully studying the field and doing some laboratory work on various processes that had been suggested, it was decided that the electrolysis of sulfate solutions was the most promising. We soon found, as have other investigators, that the only way to obtain a good zinc deposit is to have the electrolyte free from all metals more electro-negative than zinc, such as copper, cadmium, lead, arsenic, antimony, etc. Arsenic and antimony are particularly injurious, causing very poor current efficiency and small yield per horsepower when present in amounts so small as almost to defy detection-1 mg. or less per liter.

Jan 10, 1920

J. L. McK. YARDLEY,* Pittsburgh, Pa. (written dlscussion ?) .-It is interesting to observe how closely Mr. Hansen agrees with other investigators to the effect that the art of electrolytic zinc has left the realm of mystery. In his introduction, lie has said practically what Thomas French said in his paper "The Future of Electrolytic Zinc. "1 The successful electrolysis of zinc from sulphate solutions has not been an easy matter, and it is only within recent years that the difficult problem of depositing high-grade zinc has been satisfactorily: accomplished on a commercial basis. The principal requisite is. that the electrolyte shall be quite free from certain impurities. The methods by which freedom from these impurities is assured are now very well understood, and with experienced superintendents there is little difficulty in obtaining a high efficiency in that part of the process. When certain underlying principles are recognized, the difficulty encountered in dealing with the filtration of the acid and slimy solutions also largely disappears, although it has been a very serious one to the uninitiated. In the dissolving of the zinc from the roasted ore, there is nothing which any competent chemical' engineer cannot undertake, and any other operations connected with the electrolytic process are either of little or no difficulty, or are common to the retort process. Mr. Hansen also agrees with R. G. Hall's statement in " Some Economic Factors in the Production of Electrolytic Zinc:"2

Jan 10, 1918

By E. B. Ekren, F. C. Frischknecht

Recently released results of surveys employing the slingram and turam methods show the applicability of electrornagnetics in mapping new areas containing both oxidized and unoxidized iron in the Lake Superior region.

Jan 10, 1961