Lithium from brines

The extraction of lithium from brines in the USA (Utah, Nevada), Chile, Bolivia and Argentina is becoming increasingly important. In these proce.sses lithium precipitates out as the poorly soluble lithium carbonate, as a byproduct in the production of other salts (borax, potassium salts, sodium chloride and magnesium chloride). 

Amorphous aluminum oxide has recently been proved to extract lithium from brines and bitterns having lithium concentrations of 0.83 and 13.1 mg/1, respectively. The sorption may be explained by the formation of hydrous lithium aluminum oxide. The sorption capacity of amorphous hydrous aluminum oxide was found to be 4.0 mmol/g. For brines and bitterns the lithium concentration factors on the sorbent attained values of 370 and 130, respectively equilibrium was reached after 7 days. The desorption of lithium ions was carried out with boiling water yielding a maximum concentration factor of lithium in the eluate of 46 in reference to the initial lithium concentration of the brines. Lithium was separated from the eluates by solvent extraction with cyclohexane containing thenoyltrifluoracetone and trioctyl-phosphine oxide, subsequent back extraction with hydrochloric acid, and precipitation of lithium phosphate by addition of K3P04. The purity of the precipitate amounted to at least 95% I7 21). 

Lithium carbonate from brines (i.e., solar evaporation processf. The recovery of lithium from brines is a less energy-intensive process and it is therefore extensively used where natural brines are found. Nevertheless, the methods of recovery used vary with the nature of the brines, especially the lithium concentration and the concentration of interfering cations such as magnesium and calcium. Brines are pumped from natural ponds (e.g., Chile, Argentina,... 

Chemetall Foote Corp. (formerly Cyprus Foote Company, wholly ovmed subsidiary of Chemetall GmbH), first company to produce lithium from brines Chemetall GmbH... 

The types of lithium - containing brines and technical solutions. Industrial technologies of the lithium recovery from brines. The selective extraction methods of lithium from brines and liquid wastes... 

The application of well crystalline and disordered LADH-CI as a reversible selective sorbent for the extraction of lithium from brines and technological wastes... 

R.L. Retallack, Electrolytic recovery of lithium from brines, US Patent No. 

A very large number of articles and patents have been issued on methods to precipitate or adsorb lithium from brines, but by far the most common is the suggested adsorption or co-precipitation of lithium on aluminum hydroxide or alumina. When aluminum chloride is added to a neutral or basic solution containing lithium most of the lithium joins the voluminous aluminum hydroxide gel-like precipitate. In a similar manner, hydrated aluminum hydroxide can adsorb lithium, and a wide range of mixtures with aluminum hydroxide (either in a solid phase or as a co-precipitate) can act in a similar manner. This method was first proposed by... 

Production of Lithium Salts from Salar de Atacama Brine. Informacion Tecnologica 9(2), 245-251. Bukowsky, H., Uhlemann, E., and Steinbom, D. (1991). The Recovery of Lithium from Brines Containing more Calcium than Magnesium. Hydrometallurgy 27, 317-325. 

Ryabtsev, A. D., Menzheies, L. T., and Ten, A. V. (2002). Sorption of Lithium from Brine into Granular LiCl-2Al(OH)3-m H2O Sorbent under Dynamic Conditions. Russian J. Appl. Chem. 75(7), 1069-1074. 

Lithium is presently being recovered from brines of Searles Lake, in California, and from those in Nevada. Large deposits of quadramene are found in North Carolina. The metal is produced electrolytically from the fused chloride. Lithium is silvery in appearance, much like Na and K, other members of the alkali metal series. It reacts with water, but not as vigorously as sodium. Lithium imparts a beautiful crimson color to a flame, but when the metal burns strongly, the flame is a dazzling white. 

Brine Sources. Lithium occurs naturally in brines from salars, saline lakes and seawater, od-fteld waters, and geothermal brines. Of these sources, lithium is produced only from brines of two salars. 

Recovery from Brines. Natural lithium brines are predominately chloride brines varying widely in composition. The economical recovery of lithium from such sources depends not only on the lithium content but on the concentration of interfering ions, especially calcium and magnesium. If the magnesium content is low, its removal by lime precipitation is feasible. Location and avadabiHty of solar evaporation (qv) are also important factors. 

The main metals in brines throughout the world are sodium, magnesium, calcium, and potassium. Other metals, such as lithium and boron, are found in lesser amounts. The main nonmetals ate chloride, sulfate, and carbonate, with nitrate occurring in a few isolated areas. A significant fraction of sodium nitrate and potassium nitrate comes from these isolated deposits. Other nonmetals produced from brine ate bromine and iodine. 

Occurrence. Numerous brines contain lithium in minor concentrations. Commercially valuable natural brines are located at Silver Peak, Nevada (400 ppm) (40,41), and at Seades Lake, California (50 ppm) (42,43). Great Salt Lake brine contains 40 ppm and is a source not yet exploited. Seawater contains less than 0.2 ppm. Lithium production started at Silver Peak in the 1970s. The concentration of lithium in the brine is diminishing, and now the principal production occurs from brine in the Salar de Atacama, Chile. 

Recovery Process. Lithium is extracted from brine at Silver Peak Marsh, Nevada, and at the Salar de Atacama, Chile. Both processes were developed by Foote Mineral Corp. The process at Silver Peak consists of pumping shallow underground wells to solar ponds where brines are concentrated to over 5000 ppm. Lithium ion is then removed by precipitation with soda ash to form a high purity lithium carbonate [554-13-2]. At the Atacama, virgin brine with nearly 3000 ppm lithium is concentrated to near saturation in lithium chloride [7447-41 -8]. This brine is then shipped to Antofagasta, Chile where it is combined with soda ash to form lithium carbonate. 

Economic Aspects and Uses. In 1976, one-third of the lithium produced in the United States was extracted from brines of Seades Lake and Silver Peak (44,45). Since then, lithium production at Seades Lake has been discontinued and the lithium concentration at Silver Peak is decreasing. During the 1980s lithium extraction was started at the Salar de Atacama, Chile. This is the largest lithium production plant in the wodd using brine as its raw material. 

There has been much interest in making chemicals from brine because of the low expense compared to alternative methods. Lithium, for example, had been mostly produced from spodumene ore, but now most is produced from brine. Those now producing from ore are seriously researching brine reserves and contemplating converting to brine sources before the turn of the century. Similady, solar salt has cost advantages over mined rock salt. Potassium chloride produced from brine has more than doubled from 1980 to 1990. 

Rona and Schmuckler [410] used gel permeation chromatography to separate lithium from Dead Sea brine. The elements emerged from the column in the order potassium, sodium, lithium, magnesium, and calcium and it was possible to separate a lithium-rich fraction also containing some potassium and sodium but no calcium and magnesium. 

Chemicals from brine, 5 784-803 calcium chloride, 5 793-795 iodine, 5 795—796 lithium, 5 796-797 magnesium compounds, 5 797-798 minerals from brine, 5 790-793 potassium compounds, 5 798-799 recovery process, 5 786-790 sodium carbonate, 5 799-800 sodium chloride, 5 800-801 sodium sulfate, 5 801-802 Chemicals Guideline, integrated,... 

Lithium is contained in minute amounts in the mineral ores of spodumene, lepidolite, and amblygonite, which are found in the United States and several countries in Europe, Africa, and South America. High temperatures are required to extract lithium from its compounds and by electrolysis of lithium chloride. It is also concentrated by solar evaporation of salt brine in lakes. 

From an economic point of view, today the majority of lithium-carbonate production comes from lithium-rich brines spodumene and, to a lesser extent, petahte ore concentrates are only mined for use in the glass and ceramic industries. Five major companies control the world s supply of lithium-mineral concentrates. 

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