Fluorine is a poisonous halogen, and the most chemically reactive of all the elements. Fluorspar (calcium fluoride) is used directly or indirectly to manufacture such products as aluminum, gasoline, insulating foams, plastics, refrigerants, steel, and uranium fuel. Most fl uorspar consumption and trade involve either acid grade (also called acidspar), which is greater than 97% calcium fl uoride (CaF2), or subacid grade, which is 97% or less CaF2. Subacid grade includes metallurgical and ceramic grades and is commonly called metallurgical grade or metspar.
Domestic Production and Use: In Illinois, fluorspar was processed and sold from stockpiles produced as a byproduct of limestone quarrying. Byproduct calcium fluoride was recovered from industrial waste streams, although data are not available on exact quantities. Domestically, production of hydrofluoric acid (HF) in Louisiana and Texas was by far the leading use for acid-grade fluorspar. HF is the primary feedstock for the manufacture of virtually all fluorine-bearing chemicals and is also a key ingredient in the processing of aluminum and uranium. Other uses included as a flux in steelmaking, in iron and steel casting, primary aluminum production, glass manufacture, enamels, welding rod coatings, cement production, and other uses or products. An estimated 68,000 tons of fluorosilicic acid (equivalent to about 120,000 tons of 92% fluorspar) was recovered from phosphoric acid plants processing phosphate rock. Fluorosilicic acid was used primarily in water fluoridation.
Recycling: A few thousand tons per year of synthetic fluorspar is recovered—primarily from uranium enrichment, but also from petroleum alkylation and stainless steel pickling. Primary aluminum producers recycle HF and fluorides from smelting operations. HF is recycled in the petroleum alkylation process.
Import Sources (2006–09): Mexico, 47%; China, 40%; South Africa, 9%; and Mongolia, 4%.
Events, Trends, and Issues: World fluorspar demand showed some signs of recovery in 2010, but was still depressed compared with that of 2008. Prices were higher compared with those of 2009 but were still far below their peak in late 2008. Market conditions improved enough that some African fluorspar mines, which were forced to shut down in 2009 because of low demand and low prices, were able to resume production in 2010.
With the dramatic decrease in fluorspar exports from China in recent years, companies outside of China were attempting to replace lost Chinese export supplies by expanding capacity at current mines or by developing new fluorspar mining projects. For example, Mexico’s second leading fluorspar producer was developing new fluorspar mining concessions that were expected to be in production by the end of 2010. The new operations would increase the company’s annual acidspar capacity by between 30,000 and 40,000 tons.
Development work continued on the new U.S. fluorspar mine in western Kentucky, which was expected to begin production in early 2011 and produce about 50,000 tons of fluorspar per year. Work proceeded on reopening the St. Lawrence fluorspar mine in southeastern Newfoundland, Canada, with planned output of 120,000 to 180,000 tons of fluorspar per year. Some exploration activities were ongoing, particularly in Sweden, but development or exploration work on other projects was slowed by lagging demand and lack of investment capital.
Fluorspar was included in the list of 14 raw materials labeled as “critical” by an expert group chaired by the European Commission of the European Union (EU). The EU faces a potential shortage of these materials, which have high supply risks because a large share of the worldwide production comes from a handful of countries. This concentration of production is compounded by low substitutability and low recycling rates.
The list was established in the framework of the 2008 EU Raw Materials Initiative, and the results of the report were expected to be used to help form strategies to ensure future access to critical raw materials. The expert group recommended updating the list of EU critical raw materials every 5 years and enlarging the scope for criticality assessment; policy actions improving access to primary resources; policy actions making recycling of raw materials or raw material-containing products more efficient; encouraging substitution of certain raw materials, notably by promoting research on substitutes for critical raw materials; and improving the overall material efficiency of critical raw materials.
World Resources: Identified world fluorspar resources were approximately 500 million tons of contained fluorspar. The quantity of fluorine present in phosphate rock deposits is enormous. Current U.S. reserves of phosphate rock are estimated to be 1.0 billion tons, which at 3.5% fluorine would contain 35 million tons of fluorine, equivalent to about 72 million tons of fluorspar. World reserves of phosphate rock are estimated to be 18 billion tons, equivalent to 630 million tons of fluorine and 1.29 billion tons of fluorspar.
Substitutes: Aluminum smelting dross, borax, calcium chloride, iron oxides, manganese ore, silica sand, and titanium dioxide have been used as substitutes for fluorspar fluxes. Byproduct fluorosilicic acid has been used as a substitute in aluminum fluoride production and also has the potential to be used as a substitute in HF production.
Fluorine Producers Arkema (EPA: AKE)
Canada Fluorspar (CVE: CFI) - St. Lawrence Fluorspar Mine in Newfoundland, Canada
Core Metals Group - Aurora, Indiana
DuPont (NYSE: DD) - http://www2.dupont.com/PFOA/en_US/ - The global leader in fluorine chemistry. You might recognize their famous fluorocarbon, Teflon.
Eurasian Natural Resources - Doornhoek fluorspar project in South Africa
Hastie Mining and Trucking - Klondike II Mine project in Livingston County, Kentucky
International Isotopes (OTC: INIS) - http://www.intisoid.com/?page_id=6 - Fluorine extraction from depleted uranium hexafluoride. They also produce radiochemical products such as barium-133, cobalt-57, cobalt-60, and iodine-131.
J.R. Simplot Co.
Kenya Fluorspar Company - operated a fluorspar mine in Kerio Valley, Kenya
Linde Group (ETR: LIN)
Lotus Resources - exploration and development of fluorspar deposits in Mongolia
Mexichem S.A.B. de C.V. - ALF3 plant in Matamoros, Tamaulipas, Mexico
Minerales y Productos Derivados - Spanish fluorspar producer
Mosaic (NYSE: MOS)
Navin Fluorine International (BOM: 532504) - http://www.nfil.in/ - Indian producer of specialty fluorochemicals and bulk fluorides
Okorusu Fluorspar - produced acid-grade fluorspar for its parent company Solvay
Potash Corp (NYSE: POT)
Sallies Ltd - Wiktop Fluorspar Mine in South Africa
Seaforth Mineral & Ore - East Liverpool, Ohio
Sephaku Holdings - Nokeng Fluorspar Mine in Gauteng Province, South Africa
Solvay SA (EBR: SOLB)
Tertiary Minerals - Storuman fluorspar deposit in Sweden and Lassedalen fluorspar project in Norway
Vergenoeg Mining
Fluorine News 2011-07-22 - (im) - SRK updates mining schedule for Sumochaganaobo fluorspar mine
2011-07-06 - (prn) - Performance fluorine chemicals and polymers
2011-06-15 - (mw) - Canada Fluorspar announces strategic agreement with Arkema resulting in a CDN$83.5 million investment to fund the St. Lawrence Fluorspar Project
2011-06-14 - (bw) - A China fluorine refrigerant industry report: Explore the capacity of China's domestic enterprises in major fluorine refrigerant products
2011-06-08 - (fci) - China's fluorine industry grows
2011-06-08 - (new) - Linde opens €2.5m eco fluorine factory in South Korea
2011-06-02 - (im) - Mongolian fluorspar "will replace" Chinese export market
2011-05-16 - (pi) - Tertiary Minerals expects quick evaluation of Norwegian fluorspar project due to extensive dataset
2011-02-22 - (sc) - Solvay secures the development of its fluorinated products by acquiring a Bulgarian fluorspar mine