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By Roberto Parra, Roberto Parada

"A novel process for minor elements control in copper pyrometallurgical production is proposed based on a theoretical analysis and the results of an experimental program. Its application can solves operational problems related to volatile elements that determine pollutants gas emissions and the final quality of anodes. The process considers a calcination of mixtures of the dust with sulfidizing agents such as dirty copper concentrate or elemental sulfur at temperature under 800 °C. The product are a clean calcine that recovers all the Cu content on the dust and a gas stream that collect the minor elements as sulfides species. The calcine can be returned to the smelter avoiding the As increasing in the circuit and so on, the capacity for the treatment of dirty concentrates for the smelter can be higher. The possibility to apply vacuum in the calcinations step can decrease the operation temperature. The solid condensed from the gas has different options for its stabilization, with the advantage that this stream represents few mass with high As content.IntroductionThe control of undesired minor elements (IVIES) in conventional pyrometallurgical copper production is especially relevant for ore deposits associated to Andes region. The concentrates that are being produced present every time higher levels of volatiles and harmful elements: group Va (As, Sb and Bi), Pb, Zn, and Sn."

Jan 1, 2008

By Jin Qiu

Experiments were performed to determine the extent of minor element elimination that occurred when mixtures of copper smelter dust and copper concentrate, were calcined under vacuum. Almost complete removal of the As, Sb, Bi and Pb occurred due to the conversion of the minor element compounds of these elements into their highly volatile sulphides by reaction with sulphur from the concentrate. Heat and mass balance calculations of the slag-blow in a copper converter found that ~30 tonnes of the vacuum calcine could be used to produce 100 tonnes of copper as white metal. The use of dirty concentrate as the sulphidizing agent in the vacuum calcination means that the minor element treatment capacity of the smelter complex could be increased by 60 %. Also the productivity of the converters may be increased by up to 8 % due to the supply of copper values and oxygen in the calcined mixture.

Jan 1, 2005

By Natasa Mitevska

The distribution coefficients of Ag, As, Au, Bi, Co, Cu, Ni, Pb, Sb, Se, Te, and Zn between copper matte and slag from the reverb furnace No.2 at the Copper Smelter and Refinery, RTB BOR (Yugoslavia), are presented in this paper. The influence of the matte grade on the minor elements distribution coefficients between copper matte and slag is analyzed. The minor elements distribution in the slag phase along the slag melt depth and the furnace length is also determined.

Jan 1, 2002

By J. F. Snyder

Minor elements determined by atomic absorption spectroscopy include: zinc, cadmium, copper, cobalt, nickel, chromium, manganese, and iron. Of these elements, only three; zinc, cadmium, and copper are found to have been introduced with the ore-forming fluids. Iron, manganese, chromium, and nickel were increased in dolo-stone lithologies when compared to limestone lithologies. The uniform distribution of cobalt suggests this element was neither increased nor decreased during ore emplacement nor during dolomitization of the rocks. Zinc increases adjacent to ore result from leakages into open spaces rather than as pervasive aureoles surrounding ore bodies.

Jan 1, 1977

By A. E. Wraith, R. Harris, J. Qiu, R. Parra

Small pilot scale experiments have shown that it is possible to almost fully eliminate the minor elements (ME), namely As, Sb, Bi and Pb contained in smelter dusts by vacuum calcination of mixtures of the dust with sulphidizing agents such as dirty copper concentrate or elemental sulphur at 900 °C and 80 +/- 30 Pa for 90 minutes. The products of this calcination are a residue comprising a purified mixture of copper containing compounds along with the gangue constituents and a high sulphur condensate comprising a mixture of the minor element compounds. In particular, the Cu:ME ratios of the concentrate and dust were increased from 250 and 50, from 28 and 12 and from 36 and 8 to roughly 3000, 3000 and 100 for the calcine, for Bi, As and Sb, respectively. It has also been calculated that (i) the copper content of the vacuum calcine may be recovered by feeding it into a Peirce-Smith converter during its slag blow, and (ii) the resulting recycling could increase the minor element treatment capacity of a smelter by 100 % while also reducing the blister As content by a factor of three. The experimental results are briefly discussed and a treated dust recycling option is examined. Example operating conditions are presented and available commercial technology for the vacuum calcination of the mixtures is reviewed.

Jan 1, 2007

By Richard D. Hagni

Mississippi Valley-type ore deposits contain significant quantities of minor elements, which are present partly in the form of separate mineral phases and partly in solid solution in the major sulfide phases for which these deposits are exploited. These elements, as separate phases, are: copper, mainly in chalcopyrite and enargite; cobalt and nickel, chiefly in thiospinels and bravoite; rare earth elements associated with certain fluorites; and native gold. Many economically important minor elements occur in solid solution in sphalerite, including silver, cadmium, iron, germanium, gallium, indium, thallium, cobalt, nickel, and mercury. Significant amounts of silver and antimony, and perhaps very small amounts of gold, are present in solid solution in galena. Chalcopyrite may contain small amounts of silver, molybdenum, bismuth, cadmium, cobalt, and nickel. Marcasite and pyrite may contain silver, thallium, cobalt, and nickel. Although some of the minor elements contained in the Mississippi Valley-type deposits are currently recovered at the smelters and refineries, many are lost in tailings, sludges, and slags; consequently, important quantities of these elements are potentially recoverable as non-conventional resources.

Jan 1, 1983

By A. J. Sinclair

One hundred and eleven pyrite samples from 3 porphyry-type deposits in the Canadian cordillera were analyzed (many in duplicate) by AA spectrophotometry for Co, Ni, Cu, Pb, Zn and Mn. All elements have density distributions that are lognormal or combinations of lognormal populations. Co and Ni in pyrites show zonal patterns that relate generally to mineralogical zones in the porphyry systems, particularly if contoured as the Co/Ni ratio. High Cu values in pyrites also correlate with Cu-rich mineralogical zones. Other elements studied appear less regular in their distribution patterns, although Zn highs in pyrite seem to occur sporadically near the margins of porphyry systems. In particular cases, pyrite geochemistry shows potential as an exploration tool to aid in target definition for detailed exploration.

Jan 1, 1976

By A. Bentzen, S. S. Wong, W. K. Fletcher, B. J. Price, A. J. Sinclair

One hundred eleven pyrite samples from three porphyry-type deposits in the Canadian Cordillera were analyzed (many in duplicate) by AA spectrophotometry for Co, Ni, Cu, Pb, Zn and Mn. All elements have density distributions that are lognormal or combinations of lognormal populations. Co and Ni in pyrites show zonal patterns that relate generally to mineralogical zones in the porphyry systems, particularly if contoured as the Co/Ni ratio. High Cu and Mn values in pyrites also correlate with Cu-rich mineralogical zones. Other elements studied appear less regular in their distribution patterns, although Pb and Zn highs in pyrite seem to occur sporadically near the margins of porphyry systems. These data considered with two other studies permit construction of an empirical model for the distribution of certain minor elements of pyrites from porphyry systems of the calc-alkalic suite. In particular cases pyrite geochemistry shows potential as an exploration tool to aid in target definition for detailed exploration.

Jan 1, 1978

By W. G. Davenport

This chapter examines three minor influences on flash smelting's industrial oxygen and oil requirements, i.e.: (a) recycle of molten converter slag to the flash furnace (b) gangue oxides and carbonates (e,g, Ah03, CaC03) in the flash furnace feed (c) minor sulfides (e.g. NiS} in the flash furnace feed. It then examines the. sensitivity of our flash furnace calculations to previously ignored aspects of smelting chemistry -Cu, S and Fe304 in slag and 0 in matte.

Jan 1, 2001

By H. D. Keiser

Minor industrial minerals included in this chapter are: the alum minerals, bromine, calcium chloride, epsomite and other natural magnesium salts, iodine, meerschaum, quartz, industrial crystals other than quartz, and nonfuel gases (air, helium, carbon dioxide). Alum Minerals The natural alums comprise a group of hydrated double sulfates, the most important of which are potash alum, KAI(S04)2.12H20, the "alum" of popular usage; ammonium alum, (NH4)AI(SO4)2, known mineralogically as tschermigite; and soda alum, NaAI(SO4)2.12H20. Kalinite, KAI(SO4)2.11H20, and mendozite, NaAl(SO4)2, 11H20, are fibrous monoclinic alums, distinct from the isometric species potash alum and soda alum.4 Alunite, KAI3(S04)2(OH)6, also known as alumstone or alum rock, has been used as a raw material in the manufacture of alum since early times. All the natural alums are highly soluble and occur as surface evaporation products in arid regions or in sheltered places. Potash alum, together with the other natural alums, commonly occurs as an efflorescence or crevice filling in argillaceous rocks and brown coals that contain disseminated pyrite or marcasite. The mineral is derived by the action of sulfuric acid, formed during the weathering of the sulfide, upon alkali-rich aluminum silicates. Ammonia alum is found chiefly in lignite or broad-coal beds and bituminous shales. Alunite is most commonly associated with acid volcanic rocks, where the rock has been largely altered and alunite formed owing to the presence of sulfuric acid solutions or vapors. Aluminum sulfate, which for most uses is the essential ingredient of alum, may be found in saline residues resulting from the evaporation of natural water and may be formed by the action of acid waters upon aluminous rocks. A deposit of natural potash alum occurs in an irregular network of veins associated with sulfur in rhyolite in Esmeralda County, Nevada, about 35 miles west of Tonopah and 10 miles north of Silver Peak. Alum was recovered at a plant operated on the property between 1920 and 1923 by crushing the ore to ¾ in., grinding to minus 80-mesh, and counter-current leaching; the resulting alum solution was then filtered and crystallized. Alunite was of much interest during World War I as a source of potash and during World War II as a source of alumina. The wellknown deposits at Tolfa, Italy, are veins in trachyte and have been the basis of alum manufacture there since the middle of the fifteenth century. Pure alunite is insoluble in water and in common acids, but if it is heated to 500°C it loses its water of hydration, and the residue consists largely of anhydrous potash alum, part of which is readily soluble in water or acids. If the heat is increased beyond 500°C, most of the sulfur combined with the alumina is released as oxides and the residue consists of potassium sulfate and alumina. Thus, either potash alum (and aluminum sulfate) or potassium sulfate and alumina may be made. In the

Jan 1, 1960

By Paul M. Tyler

MINOR industrial minerals included in this chapter are: the alum minerals, bromine, calcium chloride, epsomite and other natural magnesium salts, iodine, meerschaum, quartz, industrial crystals other than quartz (Iceland spar, tourmaline, fluorite, selenite, mica), and nonfuel gases (air, helium, carbon dioxide). ALUM MINERALS The alums comprise a series of double sulphates (or selenates) isomorphous with potash alum, which, according to a ruling of the Pennsylvania courts, is the only product commercially described simply as "alum." Common alum occurs in nature as kalinite (K2SO4- A12 (SO4) 324H2O). The mineral mendozite (Na2S04) 3.A12 (SO4)3- 24H2O) is soda alum; tschennigite (NH4)2SO4.Al2 (SO4)3.24H2O) is ammonium alum; and there are about a dozen other native alums and related double sulphates. Alunite (alumstone or alum rock) has the formula Al2(SO4) 3.K2S04.4A1 (OH)3 and alunogen, Al2(So4) 3.18H20. Saline residues, found wherever natural water is evaporated, may contain sulphate of alumina, which for most uses is the essential ingredient of alum. Mineral wells and springs that emerge from beds of pyritiferous shale are typically astringent and at times form local deposits of alum, generally as incrustations. Acid waters acting upon aluminous rocks may form sulphates of alumina. The alums of commerce, as well as aluminum sulphate (concentrated alum), are produced principally by treating bauxite with acid, but they have been made also on a substantial scale from clay, cryolite, pyritic slates, schists, lignites, alunite, and leucite. Alum shale-chiefly clay, pyrite, and (usually) carbonaceous matter-was extensively used in England as a source of alum for more than two centuries. In France, pyritic lignites mixed with sand and clay were burned in heaps to red ash, the leach Liquors from which, after treatment with ammonia, yielded alum and copperas. Processes have been developed for making alum or aluminum sulphate from such diverse materials as feldspar, aluminous phosphate minerals, greensand, and mixtures of mica and

Jan 1, 1949

By Hugh Douglas

ANTIMONY Antimony (Sb) has been used since the early Egyptian dynasties. Prior to World War I, total demand amounted to only 6000 to 7000 tons per year (tpy). Wartime uses and rapid rise of industrialization in the Northern Hemisphere nations have pushed world antimony use to the 78,000-tpy level. An overwhelming supply of low-cost antimonial resources in the Sino-Russian bloc countries has and will continue to have a major impact on availability and price to users outside the bloc. Table 14.4.1 shows trends in world production, United States production and consumption, and prices. Demand Antimony is used principally as an alloy in lead-based metals and other alloys. Pure metallic antimony usage is small and is confined to such areas as laboratory and electronic applications. Lead-antimony alloys are used in automobile storage batteries, chemical pumps, and pipes, tank linings, roofing material, and cable sheaths. The metal increases the hardness of lead, and, for such uses as foundry printing type, reduces shrinkage for casting and lowers the melting point. Antimonial oxides are used for ceramic purposes, white paint pigments, glass forming, textile finishing, fire retardants in military clothing, matches, and solder. Wartime applications include use as hardener for bullets, an element for tracer bullets, and ingredient for producing dense white smoke for visual markers. A small but rapidly growing use for antimony is for metallic compounds in semiconductors and thermoelectric devices. In the United States demand for antimony is about evenly divided between metallic end-use markets and nonmetallic markets. In metallic end uses, antimonial lead accounts for 27% of total metallic and nonmetallic use; in nonmetallic areas major uses are flame retardants (15%) which is the fastest growing market, plastics (13 % ), and ceramics and glass (11%). While antimony has advantages in most of its applications, there are uses in which other materials can be substituted, including: mercury, titanium, lead, zinc, chromium, tin, and zirconium in paints and pigments; tin in sheathings; calcium in battery plates; and bismuth in type metal. Supply Antimony is produced from both antimony ores and as a byproduct of smelting other ores. The principal ore mineral is stibnite (Sb2S3), along with its oxidized antimonial minerals and derivatives which occur in small discontinuous replacement veins or fissure vein implacements. Stibnite occurs in quartz-gold veins and copper-lead-zinc

Jan 1, 1976

By Chung Yu Wang, Guy C. Riddle

There are found in nature upward of II2 minerals containing antimony, but only a few of them, listed in Table I, can be considered as antimony ore-forming minerals. Stibnite (Sb2S3), antimony sulphide or glance, is the principal ore of antimony. The oxide ores—cervantite, kermesite, valentinite, sernarmontite—occur sparingly in nature. Dry methods are generally adopted for the extraction of the metal. Electrometal-lurgical methods have had much attention in America and Germany and have not yet found, on economic grounds, practical or extended application, except in a few places. During recent years, treatment of the poor grades of the ore, especially sulphide, by ore-dressing methods, has commanded some attention and been adopted at a few plants. The impure sulphide of antimony, resulting from the liquation process, is called lLneedle," "liquated" or "crude" anti- mony, and the refined metal itself is called antimony "regulus." The different processes for the treatment of antimony ores are shown in the diagram of Fig. I. Liquation of Crude Antimony The first step in the smelting of antimony is a simple one, the process of LLliquation," which produces crude or needle antimony. Ores containing $ 50 per cent Sb are used in the liquation process for the production of crude. The temperature required for liquation is between 550' and 600°C. Ores to be liquated are broken to about walnut size. If the pieces are larger than this, the low heat used will not penetrate' effectively, and if they are smaller the ore tends to pack too closely for adequate penetration. A packed charge also prevents the free escape of the fused sulphide. Intermittent Liquation in Crucibles The unique type of furnace that is in use in China for smelting is not highly efficient but is simple in construction and operation. The furnace is generally built

Jan 1, 1944

By H. J. Schroeder

Legislation and Government Programs.-The Occupational Safety and Health Administration (OSHA) accepted written comments until July 23, 1976, and held an informal hearing on August 24, 1976, to receive oral testimony regarding an economic and inflation impact statement prepared by OSHA on the proposed standard for occupational exposure to inorganic arsenic. These written and oral submissions were to be used in conjunction with information supplied at 1975 hearings to promulgate emission standards. An in-depth study for the Environmental Protection Agency (EPA) assembled and interpreted comprehensive information on arsenic and its compounds and the effects of these substances on people, animals, and plants.2 Another study for EPA assessed the role of arsenic and its compounds in the environment and in the economy of the United States and evaluated the need for and the projected effect of controlling its production, use, dissipation, and emission.3

Jan 1, 1978

By J. Roger Loebenstein

Small amounts of arsenic trioxide were shipped in 1988 from remaining stocks at ASARCO Incorporated's closed plant at Tacoma, WA. Imports of arsenic trioxide were at about the same level in 1988 as in the previous year. Legislation and Government Programs The Occupational Safety and Health Administration (OSHA) levied a $1.6 million fine against Asarco for exposing its workers at its East Helena lead smelter in Helena, MT, to unacceptably high levels of lead and arsenic. The bulk of the fine was for violations of a respiratory protection program. The same smelter and its environs has been listed as a Superfund toxic-waste site by the Environmental Protection Agency (EPA). Tests had shown high levels of lead, cadmium, and arsenic in the soil near the smelter. EPA planned to extend the cleanup to areas within the town of East Helena because high levels of arsenic had been found in shallow test wells outside the smelter site. Federal and State health officials have warned residents living in the vicinity of East Helena to avoid eating certain home-grown vegetables because of high concentrations of heavy metals.2

Jan 1, 1990

By Gertrude N. Greenspoon

Legislation and Government Programs.-The Occupational Safety and Health Administration (OSHA) held public hearings in early 1975 on proposed standards for exposure to inorganic arsenic. The findings obtained at the hearings will be considered to promulgate emission standards. Domestic Production.-Arsenic trioxide (As203) was produced domestically only at the Tacoma, Wash. copper smelter of ASARCO Incorporated. Production data cannot be published. Output rose 9% over that of 1974, shipments were less than half those of 1974, and stocks rose 31 %. Production of arsenic metal, begun by ASARCO in August 1974, continued in 1975.

Jan 1, 1977

By Donald M. Liddell

From a commercial standpoint, the only beryllium mineral warranting attention is beryl, 3Be.Al2O3.6SiO2, which is of fairly widespread occurrence. The chief deposits are in Brazil, Argentina, India, Canada and Portugal. When pure this contains about 14 per cent of beryllium oxide. The mineral richest in beryllium is phenacite, (BeO)2SiO2, or beryllium orth-osilicate, which contains 45.55 per cent beryllium oxide when pure, and if anyone is ever fortunate enough to discover a large deposit of it, it will revolutionize beryllium metallurgy. Gadoljnite, zBe0.Fe0.2Yz0~.zSi0~, is also often referred to as a beryllium mineral, though the occurrences are comparatively scant and it is of more interest as a source of yttrium than it is of beryllium. There has been a good deal of talk recently regarding some occurrences of helvite in the United States. Helvite is a complex manganese-iron beryllium silicate and, apart from difficulties that would arise in its treatment because of its compo-sition, the beryllium content of the known deposits is not high. Early Metallurgy The elemcnt beryllium was first isolated by L. N. Vauquelin in 1797.~ He crushed and heated beryl, having the idea that this heating made it more readily amenable to attack by chemicals, and then mixed the mineral with three times its weight of caustic potash and fused the mixture. The melt after cooling was dissolved in hydrochloric acid: dehydrated, and again taken up with hydrochloric acid and filtered to separate the silica. The filtrate was treated with an excess of potassium carbonate and the precipitate after draining was leached with a solution of caustic potash, which dissolved the alumina. The undissolved material was, in Vauquelin's own words, "une terre nouvelle." He dissolved the precipitate with nitric acid and evaporated it to dryness, took up with hydrochloric acid and threw the iron out with potassium hydrosulphide, though he found that to make a complete separation of the iron involved a second treatment. The solution, after throwing out of the iron, had a pronounced sweet taste, and though Vauquelin always speaks of working on "terre du beril" he suggests that the new element should be known as "glucine" (glucinum) from the Greek word for sweet, because of this outstanding property. Vauquelin did considerable work on the comparison of aluminum and beryllium, working out a separation of most of the aluminum based on its precipitation as alum. His work is reviewed at some length, since ordinarily his procedure is incorrectly stated. It will also be recognized by those who have studied beryllium metallurgy that a good many technicians have followed his ideas since, including preheating the beryl before treatment. The fusion with

Jan 1, 1944

By Walter Renton Ingalls

Metallurgical literature has no record of any ore beneficiated for cadmium alone, and the cadmium of commerce is derived from zinc ore, with which cadmium is generally associated. Zinc ores free from cadmium—e.g., the ores of the Franklin and Stirling mines, New Jersey, and of Broken Hill in Rhodesia—are rare. Blende concentrates of 50 to 60 per cent grade have contained (in production of important tonnage) as much as I per cent Cd, which is unusually high. The concentrates from the Tri-State district average from 0.3 to 0.4 per cent Cd, which is high. The concentrates from mines west of the Rocky Mountains seldom are higher than 0.2 per cent. In the periodic system of the elements, cadmium is in the same group with zinc. Its properties and compounds are similar. Its metallurgy is also similar. Cadmium has a melting point of 320°C. and a boiling point of 778"C., while the melting point of zinc is 415'C. and the boiling point gos°C. These conditions, together with the lower reduction temperature of cadmium oxide, indicate means for. separating cadmium from zinc. Cadmium in spelter is viewed, if not as an impurity, at least as an alloying element that may be objectionable, its special effect being hardening. However, for some purposes, a little cadmium in spelter is desired, and 0.4 per cent may be permissible, even in spelter for rolling. Cadmium in spelter for brassmaking is completely volatilized at the temperature of that process, and in bygone days an immense quantity of cadmium must have been lost in the fumes from these furnaces. Pyrometalltjrgy—Early Cadmium compounds, sulphide and oxide, being more volatile than the corresponding compounds of zinc, loss of cadmium begins to occur from the first furnace operation. In normal roasting, even with Tri-State ore, this loss may not be very high. Raw ore, assaying 0.4 per cent Cd, may be expected to give a roasted product of the same assay, which would imply a cadmium loss of about 15 per cent. Roasted ore, assaying 0.4 per cent Cd when distilled at ordinary furnace temperature, yielded spelter containing about half of that in the ore charged. The first draw of spelter under these conditions may assay 0.8 per cent Cd (accounting for 22 per cent of the cadmium recovery) and after the several draws of spelter have been equalized the cadmium content may average 0.35 per cent. If, therefore, 2000 lb. of blende averaging 0.35 to 0.4 per cent Cd is roasted and distilled, there may be obtained 1000 lb. of spelter, assaying 0.35 per cent Cd or 3.5 lb. content, which entering into Prime Western spelter will be sold at the spelter price. It will be observed from the outline hereinbefore (summarizing conditions prior to the introduction of sintering) that the main loss of cadmium occurred in the distillation process and by failure to condense, which could be ameliorated by attaching a prolong to the condenser, thus collecting

Jan 1, 1944

By C. T. Baroch

CESIUM-137 ISOTOPE began to displace cobalt-60 III the treatment of cancer during 1956. Production and Consumption.-Consumption of cesium and rubidium was approximately the same as in 1955. Production, however, decreased, as several companies shipped from stocks produced in previous years. South Africa was the source of most cesium and rubidium minerals used in the United States in 1956. Cesium and rubidium metals and compounds were produced from ore by: DeRewal International Rare Metals Co., Philadelphia, Pa.; Fairmont Chemical Co., Inc., Newark, N. J.; Foote Mineral Co., Philadelphia, Pa.; and Rocky Mountain Research, Inc., Denver, Colo. Most sales were to domestic consumers, but small quantities were exported to Australia, England, Germany, and Sweden. New production facilities were under construction in. 1956 by San Antonio Chemicals to produce mixed potassium, rubidium, and cesium carbonates. A plant capable of separating and packaging 200,000 curies of cesium-137 annually was under construction at Oak Ridge National Laboratory.6

Jan 1, 1958

By Charles T. Baroch

RESEARCH strengthened the position of cesium as the preferred material (commonly but erroneously called "fuel") for ionic propulsion engines. Its use as an element of the plasma thermocouple for generating electricity also seemed more likely. Domestic Production.-No domestic ore of cesium and rubidium was produced. San Antonio Chemicals, Inc., San Antonio, Tex., and Maywood Chemical Works, Maywood, N.J., continued to produce cesium and rubidium compounds including carbonate, chromate, hydroxide, nitrate, sulfate, and all four halides. Rocky Mountain Research, Inc., Denver, Colo., began producing various cesium and rubidium salts. American Potash & Chemical Corp., Los Angeles, Calif., offered cesium and rubidium for sale.

Jan 1, 1960