Search Documents

By H. G. Wickes

Virtually all fluorine consumed by the aluminum industry is as the electrolyte of the Hall-Heroult process for producing primary aluminum. A small amount of fluorspar is used but most fluorine is consumed as either aluminum fluoride or cryolite. Some fluorine- containing materials are used in secondary aluminum production, but the amount is negligible compared with primary production requirements. Any analysis of the future of the primary aluminum industry must take into account two powerful and closely related driving forces which are shaping that future. These factors are increasingly stringent restrictions on the emission of pollutants and the continuing cost-price squeeze. Nowhere do these factors combine more forcefully than in the area of fluorine consumption. We can safely assume that industry efforts to reduce fluorine consumption will be intensified and that these efforts will be fruitful. This paper will attempt to identify and quantify the factors and trends of fluorine consumption during the next decade. We will be concerned primarily with the demand for new fluorine. Sources of new fluorine will not be treated.

Jan 1, 1973

By Harold R. Bradford

EXPANSION initiated during and after the war has placed industrial plants in new areas and increased reduction and manufacturing facilities in communities already established. With added expansion interest has grown in possible area contamination from waste products. Evolved flue waste contains many chemical contaminants that may or may not cause concern; however, atmospheric pollution has always been a problem to industrial communities. For some time effects attributed to small quantities of compounds of fluorine in various waste gases have been studied by industrial, medical, agricultural, and associated interests.1,2 Aside from an article by Churchill, Rowley, and Martin in 1948,3 little has been published on the subject of fluorine in coal except by foreign investigators.

Jan 1, 1957

By Haskiel R. Shell

While the original purpose of the Bureau of Mines work on fluorine micas was to synthesize large single crystals or film suitable to replace natural muscovite or phlogopite, the objective was broadened to include development of the many possible fluorine micas as a class of new, unique materials. Several methods were developed for the synthesis of the fluorine micas at atmospheric pressure: Solid state reaction, melting in crucibles, internal resistance electric melting, and arc resistance electric melting. The latter two methods are now med commercially. A variety of fluoromicas were synthesized by isomorphic substitution including disilicic, trisilicic, and tetrasilicic. Fluorophlogopite, KMg3AlSi3O10F2, is the fluoromica most widely used. While most of the fluoromicas are completely stable to water, many water-swelling fluoromicas and fluoromontmorrilonoids were synthesized. Single crystals or film of the fluorine micas were grown to 2 inches or more by a number of methods, but none has as yet proved economical. In the report, detailed data and descriptions are given on compositions, syntheses, products, and uses, and on the properties including physical, dielectric, chemical, X-ray, optical, and structural.

Jan 1, 1969

By J W. Glatthaar, M Mavotoi

The occurrence of fluorine in the copper/gold concentrates produced by Ok Tedi Mining Limited has provided a series of challenges to metallurgists since 1988. Although fluorine is distributed throughout the gangue minerals contained within Ok Tedi ores, itsÆ presence in talc and phlogopite (naturally floating fluorosilicates) has proven to be the predominate sources of fluorine in the final concentrate. Initial treatment for the fluorosilicates consisted of the use of a carboxy-methyl cellulose depressant added to the flotation cleaners. This was superceded in 1998 with the installation of a fluorine reverse flotation process for the removal of naturally floating fluorosilicates from the final concentrate when the fluorine content of the final concentrate exceeds smelter-defined trigger points. The fluorine reverse process is similar to by-product molybdenite concentrate production in that sodium hydrosulfide is used to depress copper/gold flotation whilst allowing the fluorosilicates to float. The process was installed in two parallel modules (to match the existing grinding/flotation modules at Ok Tedi), each consisting of a closed rougher/cleaner circuit configuration. Both rougher and cleaner cells are Jameson Cells from MIM Process Technologies, with the selection based on both processing characteristics and available construction space. This paper discusses both the nature of fluorine in-, and its removal from-, Ok Tedi copper/gold concentrates.

Jan 1, 2003

By P. L. Crouse

"SynopsisFluorine – in the form of hydrofluoric acid, anhydrous hydrogen fluoride, elemental gaseous fluorine, fluoropolymers, volatile inorganic fluorides, and more – has played, and still plays, a major role in the nuclear industry. In order to enrich uranium, the metal has to be in the gaseous state. While more exotic methods are known, the standard and most cost-competitive way of achieving this is by means of uranium hexafluoride (UF6). This compound sublimates at low temperatures, and the vapour is enriched using centrifugal processes. The industrial preparation of uranium hexafluoride requires both elemental fluorine gas and anhydrous hydrogen fluoride (HF). HF is prepared by the reaction of sulphuric acid with fluorspar (CaF2). Fluorine gas in turn is prepared by the electrolysis of HF. Yellowcake is first converted to uranium tetrafluoride (UF4), using HF, after which the compound is treated with fluorine to yield UF6. After enrichment, the UF6 is reduced to UO2 for use in fuel elements in pellet form.South Africa has the largest reserves of fluorspar internationally, and is the third largest producer after Mexico and China. Fluorine technology has many associated difficulties, because of the reactivity of fluorine and the toxicity of HF. The main barriers to entry into the fluorochemical industry are thus the abilities to produce both HF and F2. Both these substances are produced locally, at the industrial scale, at Pelchem SOC Ltd. Should South Africa contemplate developing its own nuclear fuel cycle as part of the awaited new-build nuclear project, it will be imperative to leverage the existing skills with respect to fluorine technology, resident at both Pelchem and Necsa, for this purpose. This paper summarizes the fluorochemical skills developed locally over the past several decades, and suggests strategies for maintaining the technology base and developing it for the next generation of scientists and engineers.IntroductionFluorine chemistry has always had a very close relationship with the nuclear industry. Although the first mention of fluorspar was recorded in the sixteenth century, and the fundamentals had been well-developed by the Second World War, it was only during the Manhattan Project (Banks et al., 1994), when almost unlimited funds were made available for the large-scale industrialization of fluorine and related compounds, that the technology took off. Expertise in both the chemistry and the engineering aspects of fluorine is essential for the design and running of several of the unit processes in the nuclear fuel cycle."

Jan 1, 2015

By Miguel Álvarez Uriarte

El presente texto describe la producción, consumo, comercialización, importaciones, exportaciones y el ácido fluohídrico de la fluorita. El espato flúor o fluorita es un mineral no metálico libre de impurezas que contiene 48. 7% de flúor y 51.3% de calcio y se presenta de forma cristalizada y en diferentes coloraciones. De acuerdo al contenido de fluoruro de calcio, varían sus calidades y usos tales como: fundente de metales para aumentar la fluidez del acero fundido; industria de vidrio por sus propiedades opalecentes y colorantes; la industria de esmaltado en el acabado de estufas, refrigeradores, mosaicos; la industria de la cerámica para darle un aspecto vidrioso a las vajillas; y el grado óptico para la fabricación de lentes por el bajo índice de refracción y débil poder disperso de los colores.

Sep 1, 1975

By Miguel Álvarez Uriarte

Como consecuencia de las bajas cotizaciones internacionales que hubo para la fluorita en la primera mitad del decenio de 1960, su producción creció lentamente respecto a los requerimientos del consumo mundial. Dicha escasez se reflejó en una recuperación de los precios y fue suficiente incentivo, junto con otros factores, para que la producción mundial del metaloide aumentará notablemente en 1971. En ese sentido, el presente texto describe el panorama de la fluorita en México a través del Instituto Mexicano de la Fluorita y así obtener información actualizada sobre el mercado y producciones mundiales, la situación de proyectos mineros de fluorita en otros países y sobre el desarrollo y usos de sustitutos de la fluorita.

Nov 1, 1975

By Thomas L. Watson

MY thanks are due to Mr. Frank Firmstone, Easton, Pa., who has called my attention to the statement in my papers that " Barite, fluorite and quartz, though not observed in the Tennessee area," . . . as possibly misleading to the reader, if construed to mean that such a discovery had never been made. Mr. Firmstone is correct in assuming that this statement referred only to the study of the worked areas of the metallic ores, especially zinc, made in the course of the survey upon which my paper was based. The occurrence of barite and fluorite with lead-ores in Tennessee was reported by Prof. Safford,2 in 1869, and by Safford and Killebrew,3 in 1887, with the further statement that about 1,000,000 lb. of barite were annually mined in Greene, Washington and Jefferson counties, Tenn., and that considerable deposits occur also in McMinn, Smith and other counties. It is also noted that the barite ".usually occurs in veins, associated with galena." The present worked areas of barite are, however, distinct barite propositions, without workable quantities of either lead or zinc, so far as mining operations have gone, and the areas are more or less removed from the present areas of zinc-ores. Mr. Firmstone informs me also that, in 1892, he observed, in the magnesian limestone at Watauga Point, in Carter county, on the left bank of the Watauga river, a little below the mouth of Buffalo creek, small quantities of galena and some fluorite.

Jan 1, 1907

By Z. D. Hora

The major fluorite producer in British Columbia was the Rock Candy Mine, inactive since 1942. Other deposits of economic interest include the Rexspar deposit, in which fluorite is associated with uranium and rare earth mineralization, and the Eaglet and Liard River occurrences. THE former Rock Candy fluorite mine, located 26 km north of Grand Forks, is the only major past producer of fluorite in British Columbia. The deposit was in production from 1918 to 1929 and again in 1942; total output was about 36,000 tonnes with average grade between 22 and 32 per cent CaF2. The fluorite body occupies a steeply-dipping vein structure, approximately 175 m long and up to 12 m wide, in porphyritic syenite. The chief vein-filling minerals are quartz and fluorite with local small len ses of barite. Fluorite content decreases with depth and the deposit becomes silicified. The Rexspar (or Birch Island) fluorite deposit is located 130 km north of Kamloops. The deposit is complex with rare earth elements and high uranium values, but !1uorite mineralization forms an independent zone adjacent to the uranium orebodies. Fluorite is present as fine-grained impregnations and as breccia cement in strongly schistose or brecciated alkali feld spar porphyry. Reported reserves are 1,088,000 tonnes of 22 per cent CaF2 or 450,000 tonnes of 29 per cent CaF2. 268 Another potential deposit of fluorite is Eaglet, situated on the north side of Quesnel Lake. Fluorite occurs as a stock work with scattered veins and irregular lenses up to 20 centimetres wide and as impregnations in altered Proterozoic Kaza Group feld spathic gneiss over an area of 1,500 metres by 500 metres. To date (1983) approximately $2 million have been spent on the exploration of this property and reserves of 18.8 mimon tonnes grading 11.59 per cent CaF2 have been outlined . A group of significant occurrences is known from north of Liard River Hot Springs Park , where fluorite occurs in small zones up to 17 m thick along the interface between Middle Devonian Dunedin Formation limestone and Middle Devonian to Mississippian Besa River Formation argillite. Fluorite, associated with witherite, barytocalcite and barite, is present as replacement bodies, breccia fillings and minor veins.

Jan 1, 1984

By P. R. A. Andrews, R. K. Collings

"There are more than 300 occurrences of fluorite in Canada. Deposits of economic significance, however, are confined to Newfoundland and Nova Scotia in eastern Canada, Ontario in central Canada, and British Columbia in western Canada. Fluorite has been mined and processed intermittently in Ontario and Newfoundland until November 1990, when Canada's only producer Minworth Ltd., a U.K. based company, with a mine and concentrator near St. Lawrence on the Burin Peninsula, Newfoundland, closed its operation.CANMET has processed ore samples from each of the major mineralized areas, and thirty-one studies were conducted between 1920and 1970. A summary of the important aspects of the various testwork studies is presented. The production of acid-grade fluorite was possible by flotation, and ceramic-grade, by flotation and gravity concentration methods. Gravity concentration methods included heavy media separation, jigging and tabling. Flotation was by direct and reverse techniques; associated minerals, quartz, calcite, barite, etc. were depressed by a variety of depressants. The function of the major depressants is discussed briefly. The various uses offluorite which include hydrofluoric acid, chlorofluorocarbons, aluminum production, petroleum alkylation, fluxing and ceramic applications etc. are discussed briefly."

Jan 1, 1993

By R. B. Strathmore Cooke, Eugene L. Talbot

The perfluoro acids and derivatives show unusual surface-active properties that qualify them as possible flotation reagents. They lower the surface tension of water from 15 to 20 dynes below that obtainable with the corresponding hydrocarbon compounds. Fluorochemicals adsorb very strongly on solid surfaces to give films that exhibit larger contact angles than films of the corresponding hydro-carbons. The large contact angles probably result from the terminal –CF3 group. The perfluoro acids are made by electrolysis of the corresponding carboxylic acid in anhydrous hydrogen fluoride. From the perfluoro acids many derivatives may be obtained, such as amides, amines, alcohols, xanthates, ethers and esters and others.

Nov 1, 1955

By S. L. Weber, V. Castranova, D. E. Banks, J. K. H. Ma, Y. Rojanasakul, J. Y. C. Ma, M. Bhat

"The mechanism of bleomycin-induced pulmonary fibrosis is not ye: clear. Recent studies have shown that alveolar macrophages (AM) can be stimulated by bleomycin in vitro releasing inflammatory cytokines, suggesting that the interaction of bleomycin with AM is an important step in the drug-induced fibrotic process. Bleomycin is known to bind DNA and generate oxygen radicals through complexation with Fe2+ and oxygen. To provide,more insight into the cellular oxidative property of bleomycin, v.s have developed a fluoromicroscopic method using 2',7'-dichlorofluorescin diacetate (DCFHDA) as an oxidative fluorescence probe to study the deomycin-induced intracellular oxidation in rat AM and the inhibition of the oxida¬tion by taurine, a compound known to inhibit the bleomycin-induced fibrosis. Bleomycin at 5 to 20 ug/ml has a moderate stimulatory effect (1.87- to 2.66-fold) on the secretion of superoxide anion. A high concentration of bleomycin (20 ug/ml), however, inhibits cell response to zymosan-induced secretion of superoxide anion. At 4 ug/ml, bleomycin has no effect on cell membrane integrity or morphology but results in a significant increase in intracellular oxidation. This oxidative process is Fe2-,-dependent and is accompanied by an increase in intracellular calcium (35 nM). Both the intracellular oxidation and calcium rise induced by internalized bleomycin are inhibited by pretreatment of cells with varying concentrations of taurine (25, 125, and 187.5 uM). The inhibitory effect on intracellular oxidation .vas found to be 36, 57, and 60%, respectively. These results demonstrate a stimulation-inhibition relationship between bleomycin and taurine on re cellular oxidation at a subcytotoxic dose of bleomycin, suggesting that the oxidative effect of the intracellular bleomycin-Fe2 complex is important in the initiation of the fibrotic process. — Environ Health Perspect 102 (Suppl10):91-96 (1994) IntroductionThe pulmonary system is most susceptible to oxygen radical-induced diseases due to its constant exposure to the highest oxygen tension, and the potential encounters with oxidant gases such as ozone, nitrogen oxides, and toxic doses of dust particles. The lung is also a well-perfused organ and thereby vulnerable to the effect of circulating xenobiotics such as paraquat, and, bleomycin, which is known to cause pulmonary injuries (1). Alveolar macrophages (AM), which act as a means of defense by phagocytizing inhaled dust particles and microorganisms while increasing production of reactive oxidative species, have been shown to play an important role in mechanisms leading to oxidative lung injury and fibrosis (2-4)."

Dec 1, 1995

By Henry Siegmann

HISTORY OF PRODUCTION AND USE In 1899 the consumption of fluorspar in the United States was reported as 16,000 tons. The invention of the open-hearth method of steel manufacture, plus the beginnings of a fluorine chemical industry, pushed consumption of fluorspar to 250,000 tons by 1918. In contrast to these consumption statistics of the past, the most recent statistics available (1972) indicate a total fluorspar usage in the United States of 1.352 million st (Table 15.4D.1). Fluorspar remains the world's cheapest source of fluorine, and its unique properties make the mineral the most desirable fluxing agent for steel refining. The linking of fluorine with carbon in the late 1930s resulted in the production of fluorocarbon, and constant growth in production over the years has formed the backbone of a strong fluorine chemical industry. For example, in 1972 it is estimated that total fluorocarbon production amounted to 2.113 million tons, and that, in this process, over 1.351 million tons of acid-grade fluorspar was consumed. The producers of primary aluminum long have been concerned about the fast dwindling reserves of natural cryolite. They found the solution to their problem by utilizing fluorspar for the manufacture of synthetic cryolite and aluminum fluoride. Nuclear weapons, as well as the growing number of peaceful uses for atomic reactors, constitute a market for uranium hexafluoride. This chemical and chlorine pentafluoride, used as an oxidizer with rocket fuels, are products that are as much a novelty as fluorocarbons were 25 years ago. Judging from past success in the field of fluorine chemistry research, it is safe to assume that the market for these chemicals will grow in the future. Three major industries account for the bulk of the fluorspar consumption: steel refining, fluorine chemical, and primary aluminum production. These industries have had a pattern of fabulous growth in the past, and their future plans point to a continuation of this pattern. It seems logical that the fluorspar usage also should continue its upward trend. Considering the growth of the fluorspar industry since 1899, and the obvious dependence on imports of fluorspar as a raw material, one of the most puzzling aspects of the past has been the apparent lack of coordination between fluorspar production and fluorspar consumption. A few authoritative voices have spoken out concerning the need to expand fluorspar production in order to meet consumption of the future. During World War II, the U.S. Government took positive steps in this direction by authorizing purchases at attractive prices for its "stockpile program." As a consequence, new fluorspar producing facilities were built, not only in

Jan 1, 1976

By Robert B. Fulton, Gill Montgomery

Fluorspar is the commercial name for fluorite, a mineral that is calcium fluoride, CaF2. The name, derived from the Latin word fluere (to flow), refers to its low melting point and its early use in metallurgy as a flux. It is the principal industrial source of the element fluorine. Two other minerals, cryolite and fluorapatite, have significant fluorine content. Cryolite, sodium aluminum fluoride, Na3AlF,, is a rare mineral that has been found in commercial quantities only in Greenland. The natural material has been supplanted by synthetic cryolite for its principal industrial use in the manufacture of aluminum. Fluorapatite, Ca5F(PO3)2, is a source of phosphate for fertilizer manufacture, containing a small percentage of fluorine. Commercially mined deposits of apatite have varying amounts of fluorine, chlorine, hydroxyl, and carbonate. HISTORY Fluorspar was used by the early Greeks and Romans for ornamental purposes as vases, drinking cups, and table tops. Various peoples, including the Chinese and the American Indians, carved ornaments and figurines from large crystals. Its usefulness as a flux was known to Agricola in 16th century Europe. Fluorspar mining began in England about 1775 and at various places in the United States between 1820 and 1840. Production grew substantially following the development of basic open hearth steelmaking, wherein it is used as a flux. Use was stimulated by growth of the steel, aluminum, chemical, and ceramic industries, particularly during World Wars I and 11. Fluorocarbons entered the picture in 1931. The use of anhydrous hydrogen fluoride (HF) as a catalyst in the manufacture of alkylate for high octane fuel began in 1942. Differential flotation for separating fluorspar from galena, sphalerite, and common gangue minerals in the 1930s and the application of heavy media concentrating methods to the treatment of low grade ores in the 1940s were outstanding technological advances that facilitated increased production. Pelletizing and briquetting of flotation concentrates for use in steel furnaces and the development of flotation schemes for beneficiating ores containing abundant dolomite and barite have been major improvements in the industry. USES OF FLUORITE Fluorspar is used to make hydrogen fluoride (HF), also called hydrofluoric acid, an intermediate for fluorocarbons, aluminum fluoride, and synthetic cryolite. It is used as a flux in the steel and ceramic industries, in iron foundry and ferroalloy practice, and has many minor specialized uses. Hydrogen fluoride is produced by reacting acid grade (97% CaF,) fluorspar with sulfuric acid in a heated kiln or retort to produce HF gas and calcium sulfate. After purification by scrubbing, condensing, and distillation; the HF is marketed as anhydrous HF, a colorless fuming liquid, or it may be absorbed in water to form the aqueous acid, usually 70% HF. Synthetic cryolite, organic and inorganic fluoride chemicals, and elemental fluorine are made from hydrofluoric acid. The acid itself is important in catalysis in the manufacture of alkylate, an ingredient in high-octane fuel for aircraft and automobiles; in steel pickling, enamel stripping, and glass etching and polishing; and in various electroplating operations. The manufacture of one ton of virgin aluminum requires about 12 to 29 kg of fluorine content in synthetic cryolite and aluminum fluoride. This quantity, through improved technology and recovery practices, is being lowered significantly in countries with the most advanced technology (i.e., Australia and Sweden), while others (i.e., Surinam and South Africa), remain at the high end. Elemental fluorine is prepared from anhydrous hydrofluoric acid by electrolysis. Gaseous at room temperature and pressure, fluorine is compressed to a liquid for shipment in cylinders or in tank trucks. Elemental fluorine is used to make uranium hexafluoride, sulfur hexafluoride, and halogen fluorides. Gaseous uranium hexafluoride is used in separating U235 from U233 by the diffusion process. Sulfur hexafluoride is a stable high dielectric gas used in coaxial cables, transformers, and radar wave guides. Halogen fluorides have important applications, mostly as substitutes for elemental fluorine, which is more difficult to handle. Emulsified perfluorochemicals, organic compounds in which all hydrogen atoms have been replaced by fluorine, are undergoing investigation as promising blood substitutes. They transport oxygen and, in conjunction with a simulated blood serum, perform many functions of whole blood. With further development, these organic compounds may ultimately, in emergencies, be useful in saving lives of animals and humans during periods of acute shortages of natural blood. Inorganic fluorides are used as insecticides, preservatives, antiseptics, ceramic additives, and fluxes and in electroplating solutions, antioxidants, and many other products. Boron trifluoride is an important catalyst. Organic fluorides are volume leaders in the fluorine chemical industry. Fluorinated chlorocarbons and fluorocarbons are prepared by the interaction of anhydrous HF with chloroform, perchlorethylene and carbon tetrachloride, and are characterized by low toxicity and notable chemical stability. They perform outstandingly as refrigerants, aerosol propellants, solvents, and cleaning agents and as intermediates for polymers such as fluorocarbon resins and elastomers. Fluorocarbon resins are inert compounds that have unusually low coefficients of friction and have found a number of applications as lubricants for parts that cannot be oiled, e.g., bearings for window raising equipment located inside of automobile doors, in small electronic equipment, for the manufacture of chem-

Jan 1, 1994

By C. B. Rash, W. W. Fowler, Gill Montgomery

INTRODUCTION Fluorspar is the common term used for the mineral fluorite, which is naturally occurring calcium fluoride (CaF2). It is the principal source of fluorine, the most reactive of the chemical elements, from which a great variety of unique and strategically important chemicals are produced. Commercial deposits of fluorspar are widespread throughout the world, and its availability is essential to the industrial progress of all nations. GEOLOGY AND MINERALOGY In its pure form fluorspar, CaF2, contains 51.1% calcium and 48.9% fluorine, and has a sp gr of 3.18 and a hardness of 4. It is commonly a glassy mineral. colorless, white, or grayish. but may also be various shades of purple, pink, blue, green, yellow, or tan. It belongs to the cubic system mineralogically, and commonly crystallizes into cubic shapes in vugs and cavities, although most of it is massive, with interlocking crystals. Minable fluorspar deposits, in descending order of importance, occur as bedded limestone replacement deposits along fault zones; fissure-filling vein deposits; breccia filling in limestones, dolomites,

Jan 1, 1985

By William I. Weisman

The annual consumption of fluorspar in the United States, in the last 10 years has doubled. In 1971, when 1,344,742 tons were consumed, almost 45 percent of this amount was used in the production of steel and nearly 50 percent was consumed in the manufacture of hydrofluoric acid. Of the hydrofluoric acid produced, about one-third was used in the manufacture of aluminum electrolytes for production of primary aluminum metal and the balance was consumed in the manufacture of a variety of fluorocarbons and other chemicals. A small amount of fluorspar, constituting less than five percent of total consumption, was used in the foundry industry, and in the manufacture of glass, enamel, cement and other products. It is apparent that a continuing supply of fluorspar will be required to meet the demands for these vital metals and chemicals in our expanding industrial society. Domestic fluorspar production meets only approximately 20 percent of our needs. Hence, it is essential that the United States maintain a healthy domestic fluorspar industry in order to have adequate domestic reserves available at times of emergency and to protect this country from becoming solely dependent on foreign sources for this strategic commodity.

Jan 1, 1973

By C. M. Bartley

Fluorspar, in addition to its familiar uses as a metallurgical flux and as a source of the electrolyte for aluminum production, has become important as an essential raw material in the rapidly growing fluorine chemical industry. The unique ability of fluorine to react and form compounds with al-most all other chemicals has made it one of the important elements in modern chemistry. Research and development over the past thirty years have resulted in a current annual production of fluorine chemicals that is both technically and economically important to industry. Because many of these chemicals and products are relatively new, and most have properties that are not duplicated by other materials, the present uses are expanding rapidly and new applications are being reported continually. Fluorspar, the only immediate and practical source of fluorine, is therefore an important mineral. This fact has been recognized in major industrial areas such as the United States and Western Europe, but has received little attention in Canada.

Jan 1, 1962

By Gill Montgomery

The strong upward curve of fluorspar consumption continued through 1968, with domestic producers unable to furnish more than 30% of U.S. requirements. Stocks of all grades were quite short at all points during most of 1968. This resulted in price increases as both domestic and foreign producers sought to cover spiralling labor costs. Further increases are probable for 1969. All Illinois mines were closed by strikes in January and February. The strong trend in metallurgical imports reflects the increased use of fluorspar in steelmaking, as new oxygen process steel plants come into production. The growth of use of all fluorocarbon chemicals continues to require additional acid grade fluorspar, with military uses a major factor. Several new aluminum smelting facilities coming into production are adding to the aluminum fluoride needs, bringing further pressure upon the world supply of acid grade fluorspar. The world-wide consumption pressure on all grades of fluorspar is pushing prices up, and no end to the tight supply is in sight, even assuming that all the new projects cited here are finished on schedule.

Jan 3, 1969

By Robert M. Grogan, Gill Montgomery

Fluorspar, the commercial name for fluorite, is a mineral composed of calcium fluoride, CaF,. Its valuable properties are due to its content of fluorine, and it is the principal commercial source of that element. The name is derived from the Latin word "fluere," to flow, because the mineral has a low melting point and is used in metallurgy as a flux. Cryolite is a sodium aluminum fluoride, Na,AlF,. It is a rare mineral which has been found in commercial quantities in only one place in the world, Greenland. Small amounts of it are shipped from stock in that country, and its place in industry has been taken over almost completely by synthetic cryolite. Because of the relative unimportance of cryolite, discussion of it has been relegated to a short section at the end of this chapter, which is principally concerned with fluorspar. History Fluorspar was used for ornamental purposes by the Greeks and Romans, who fashioned such things as vases, drinking cups, and table tops from it. Various peoples including the Chinese and the American Indians carved ornaments and figurines from large crystals. Its usefulness as a flux was known to Agricola (1564), who wrote about it in 1546. Mining began in England about 1775 and at various places in the United States during the period 1820 to 1840. Production became substantial following the development and widespread adoption of the basic open hearth method of making steel, in which fluorspar is used as a flux. After that, production and usage were stimulated by growth in the steel, aluminum, chemical, and ceramic industries and were accelerated by World Wars I and II. Fluorocarbons entered the picture in 193 1 and the use of anhydrous hydrogen fluoride (HF) as a catalyst in the manufacture of alkylate for high octane fuel blends began in 1942. The development of the froth flotation process in the late 1920s, a differential flotation scheme for separating fluorspar from galena, sphalerite, and common gangue minerals in the 1930s, and the application of heavy-media concentrating methods to the treatment of low grade ores in the 1940s were outstanding technological contributions that enabled increased production of fluorspar concentrates. In recent years the development of pelletizing and briquetting processes for making flotation concentrates into gravel-size particles for use in steel furnaces and the development of more efficient and selective flotation schemes for treating crude ores containing abundant dolomite and barite have been major improvements in the industry.

Jan 1, 1975

By Robert B. Fulton, Gill Montgomery

Fluorspar is the commercial name for fluorite, a mineral that is calcium fluoride, CaF2. The name, derived from the Latin word fluere (to flow), refers to its low melting point and its early use in metallurgy as a flux. It is the principal industrial source of the element fluorine. Cryolite, sodium aluminum fluoride, Na3AlF6, is a rare mineral which has been found in commercial quantities only in Greenland. The natural material has been supplanted by synthetic cryolite for its principal industrial use in the manufacture of aluminum. History Fluorspar was used by the early Greeks and Romans for ornamental purposes as vases, drinking cups, and table tops. Various peoples, including the Chinese and the American Indians, carved ornaments and figurines from large crystals. Its usefulness as a flux was known to Agricola in sixteenth century Europe. Fluorspar mining began in England about 1775 and at various places in the United States between 1820 and 1840. Production grew substantially following the development of basic open-hearth steelmaking, wherein it is used as a flux. Use was stimulated by growth of the steel, aluminum, chemical, and ceramic industries, particularly during World Wars I and II. Fluorocarbons entered the picture in 1931. The use of anhydrous hydrogen fluoride (HF) as a catalyst in the manufacture of alkylate for high octane fuel began in 1942. Differential flotation for separating fluorspar from galena, sphalerite, and common gangue minerals in the 1930s, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940s were outstanding technological advances that facilitated increased production. Recently, pelletizing and briquetting of flotation concentrates for use in steel furnaces and the development of flotation schemes for beneficiating ores containing abundant dolomite and barite have been major improvements in the industry. Uses of Fluorspar Fluorspar is used to make hydrogen fluoride, also called hydrofluoric acid, an intermediate for fluorocarbons, aluminum fluoride, and synthetic cryolite. It is used as a flux in the steel and ceramic industries, in iron foundry and ferroalloy practice, and has many minor specialized uses. Hydrogen fluoride (HF) is produced by reacting acid grade (97% CaF2) fluorspar with sulfuric acid in a heated kiln or retort to produce HF gas and calcium sulfate. After purification by scrubbing, condensing, and distillation, the HF is marketed as anhydrous HF, a colorless fuming liquid, or it may be absorbed in water to form the aqueous acid, usually 70% HF. Synthetic cryolite, organic and inorganic fluoride chemicals, and elemental fluorine are made from hydrofluoric acid. The acid itself is important in catalysis in the manufacture of alkylate, which is an ingredient in high-octane fuel for aircraft and automobiles, in steel pickling, enamel stripping, glass etching and polishing, and in various electroplating operations. The manufacture of one ton of virgin aluminum requires about 50 to 60 lb of fluorine content in synthetic cryolite and alumnium fluoride. This quantity, through improved technology and recovery practices, is being lowered significantly.

Jan 1, 1983