LITHIUM by Joyce A

LITHIUM By Joyce A. Ober Domestic survey data and tables were prepared by Maria Arguelles, statistical assistant, and the world production table was prepared by Regina R. Coleman, international data coordinator. Introduction carbonate produced at SQM’s brine operation. FMC determined that the supply agreement with SQM would be more economical In 2002, Chile was once again the world’s leading producer than continuing to produce lithium carbonate from its own of lithium carbonate. Production was from its two lithium brine operation in Argentina that began production in 1997 (FMC operations on the Salar de Atacama in the Andes Mountains Corp., 2001, p. 25). FMC produced lithium chloride and a and two lithium carbonate plants in Antofagasta. In the United limited amount of lithium carbonate in Argentina in 2002. States, production continued at a single lithium brine operation LithChem International (a subsidiary of ToxCo, Inc.) and lithium carbonate plant in Nevada. There was one lithium of Anaheim, CA, produced lithium carbonate and lithium carbonate plant and one lithium chloride plant in Argentina hydroxide at its plant in Baltimore, OH. LithChem produces on the Salar del Hombre Muerto; the carbonate plant operated these compounds from lithium compounds that are products below capacity. China and Russia continued lithium carbonate of ToxCo’s lithium battery recycling operation in Trail, British production. Australia, Canada, and Zimbabwe were important Columbia, Canada. Another ToxCo subsidiary, Ozark Fluorine sources of lithium concentrates. A large percentage of the Specialties Inc. in Tulsa, OK, produces hydrofluoric acid, some lithium carbonate produced in South America was exported of which is converted to lithium hexafluorophosphate, high- to the United States as feed material for the production of purity lithium fluoride, and other electrolytes used in lithium downstream lithium compounds, such as lithium hydroxide batteries (McCoy, 2002). monohydrate, lithium metal, and organic lithium compounds, Lithium carbonate is the most important lithium compound and for consumption in industrial applications. produced from brine and ore deposits. In most cases, other Many commercial lithium products are available because lithium compounds require lithium carbonate as a feedstock of lithium’s electrochemical reactivity and other unique for further processing. The only domestic producer of lithium properties. Lithium is sold as brines, compounds, metal, or carbonate from brine is Chemetall Foote’s operation in Nevada. mineral concentrates depending on the end use. Most lithium Nevada brines enriched in lithium chloride, which averaged compounds and minerals are consumed in the production of about 300 parts per million (ppm) when Foote Mineral Co. ceramics, glass, and primary aluminum. The use of organic (the original owner of the deposit) began operations in 1966, lithium compounds as industrial catalysts and the consumption are pumped from the ground and progress through a series of of various lithium compounds in lithium batteries are the most evaporation ponds (Engineering and Mining Journal, 1970). rapidly expanding markets. During the course of 12 to 18 months, the concentration of the brine increases through solar evaporation to 6,000 ppm lithium. Production When the lithium chloride reaches optimum concentration, the liquid is pumped to a recovery plant and treated with soda ash, The U.S. Geological Survey collects domestic production data precipitating lithium carbonate. The carbonate is then removed for lithium from a voluntary canvass of U.S. operations. The through filtration, dried, and shipped. A similar process is single U.S. lithium carbonate producer, Chemetall Foote Corp., used to recover lithium from the Chilean brines, with slight responded to the survey, representing 100% of total production. adjustments to account for their different chemistries. The brine Production and stock data were withheld from publication to operation in Argentina uses a different, proprietary technology avoid disclosing company proprietary data (table 1). that allows for the lithium recovery as either carbonate or Chemetall Foote (a subsidiary of the German company chloride (FMC Corp., 1998, p. 23, 25). Chemetall GmbH) produced lithium carbonate from brines Until the last domestic mine closed in 1998, spodumene had near Silver Peak, NV. The company’s other lithium operations been the major raw material used for the production of lithium included a lithium hydroxide plant in Silver Peak; a butyllithium carbonate in North Carolina, and small amounts of spodumene plant in New Johnsonville, TN; and facilities for producing concentrate were produced for sale. Spodumene is the most downstream lithium compounds in Kings Mountain, NC. common lithium mineral, but petalite and lepidolite are other FMC Corp., Lithium Division produced a full range of minerals that are mined in different parts of the world for downstream compounds, lithium metal, and organic lithium their lithium content. These three minerals are beneficiated to compounds at its facilities in Bessemer City, NC, and Bayport, produce lithium concentrates that can be used directly in certain TX. FMC operated a lithium carbonate plant and spodumene applications. mine in North Carolina until 1998. Since 1999, the company Extracting lithium from spodumene entails an energy- has met most of its lithium carbonate requirements through a intensive chemical recovery process, which is more costly than long-term agreement with Chilean producer Sociedad Quimica that used for brines. Because of the high cost of producing y Minera de Chile S.A. (SQM) to supply FMC with lithium lithium carbonate from spodumene, most lithium carbonate LITHIUM—2002 46.1 production has shifted to brine deposits. Spodumene was Perhaps more important are the environmental benefits of lithium believed to be the source of lithium carbonate production consumption at aluminum smelters, reducing fluorine emissions in China and Russia. After mining, spodumene is crushed by 20% to 30%. More modern aluminum smelters are more and undergoes a flotation beneficiation process to produce efficient and less polluting without the addition of lithium carbonate concentrate. The concentrate is heated to 1,075˚ C to 1,100˚ C, (Chemetall GmbH, 2001§). changing the crystal structure of the mineral and making it more Domestically, the third largest and the fastest growing end reactive to sulfuric acid. A mixture of finely ground converted use for lithium compounds was as catalysts in the production spodumene and sulfuric acid is heated to 250˚ C, forming of synthetic rubbers, plastics, and pharmaceuticals. N- lithium sulfate. Water is added to the mixture to dissolve butyllithium is used to initiate the reactions between styrene the lithium sulfate. Insoluble portions are then removed by and butadiene that form abrasion-resistant synthetic rubbers that filtration. The purified lithium sulfate solution is treated with require no vulcanization. Other organic lithium compounds soda ash, forming insoluble lithium carbonate that precipitates were used as catalysts for the production of plastics, such as from solution. The carbonate is separated and dried for sale polyethylene. Lithium metal and compounds also were used or use by the producer as feedstock in the production of other as catalysts in the production of an analgesic, anticholesterol lithium compounds. agents, antihistamines, contraceptives, sleep inducers, steroids, tranquilizers, vitamin A, and other products. Lithium catalysts Consumption were used in the production of protease inhibitors, important drugs in the treatment of human immunodeficiency virus type The aluminum, ceramics and glass, lubricating grease, and 1/acquired immunodeficiency syndrome (HIV-AIDS) (Schmitt, synthetic rubber industries used most of the lithium minerals 2001). Pharmaceutical-grade lithium carbonate was used in the and compounds consumed in 2002. Estimated domestic treatment of manic-depressive psychosis. This was the only consumption was stable from 1997 through 2000, but in 2001, treatment approved by the U.S. Food and Drug Administration consumption plummeted to only 50% of what it was in the 4 in which lithium was consumed by the patient. previous years. In 2002, consumption decreased an additional The multipurpose grease industry was another important market 21%, resulting in consumption of less than 40% of what it for lithium in 2002. Lithium hydroxide monohydrate was the had been only 2 years earlier. In 2001, primary aluminum compound used for the production of lithium lubricants. Lithium- production, a major end use for lithium carbonate, decreased based greases were favored for their retention of lubricating by 28% from the previous year. This production rose slightly properties over a wide temperature range; good resistance to in 2002, but not enough to have much impact on lithium water, oxidation, and hardening; and formation of a stable grease consumption (Plunkert, 2002, 2003§1). Further decreases in on cooling after melting. These greases continued to be used in estimated consumption indicated decreased lithium consumption aircraft, automotive, industrial, marine, and military applications. in other end uses, including ceramics and glass, lubricants, Almost all major battery manufacturers marketed some type synthetic rubber, and pharmaceuticals, although data to support of lithium battery. Research and development continued, and this assumption were not available. innovative rechargeable battery

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