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Alkali Metals Production (Li, Na, K) Availability and High Potential Yield of Lithium Oxide (Li2o)

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Alkali Metals Production (Li, Na, K) Availability and High Potential Yield of Lithium Oxide (Li2o) Alkali Metals Production (Li, Na, K) availability and high potential yield of lithium oxide (Li2O). Large reserves of spodumene can be found in North Carolina in the United States and in Quebec 1. Introduction and Manitoba in Canada. Spodumene theoretically contains 8.03% of Li2O. Amblygonite, (LiAl(PO4)F, Lithium (Li: atomic number 3), sodium (Na:11), and OH) contains 10.1% Li2O, and is mostly available in potassium (K:19) are very reactive, monovalent alkali Europe, Africa, and South America for commercial metals that occupy the Group 1A position on the extraction. Substantial amounts of petalite (Li2O Á periodic table. These metals find extensive applica- Al2O3 Á 8SiO2: 4.09% Li2O) and lepidolite (K2(LiAl)5–6 tions in many industries, both as pure metal as well as (Si6–7Al2–1O20): 4.89% Li2O) are also found in compounds. Application in compound forms is Rhodesia, Africa. The other nonmineral source of significant for all alkali metals, as some of the most lithium is brines. The concentration of lithium found important commercial chemicals contain these metals. in seawater is B0.1 ppm. It is also prevalent in other Lithium is used as a stearate in lubricating greases, as mineral waters such as Searles Lake in California. oxide in ceramics and porcelain, as halides in welding fluxes and as salts in medical treatment. Recent applications of lithium metal include batteries and 2.2 Extraction and Purification of Lithium energy storage devices. Aluminum–lithium alloys Flotation is primary used for mineral extraction from have found extensive use in aerospace applications. lithium ores. In this process, lithium ores are Sodium is primarily used in the synthesis of anti- concentrated with respect to lithium oxide from knock agent for automotive gasoline. Other uses 1–3% Li2O to 4–6% Li2O through heavy medium include reductant for zirconium, titanium, and potas- separation using dense nonaqueous liquids in a froth sium metal production and as a reductant of oils to flotation process. Silicate ores are most widely fatty alcohols for detergent applications. Its com- processed using the flotation method, those products pounds, particularly the chloride and hydroxide are are subsequently chemically cleaned by an acid or important industrial chemicals. Potassium in the form alkaline process. of chloride is mainly used in fertilizers. In the acid cleaning process, the concentrated The primary production method of sodium and spodumene ore is placed in a kiln and heated to lithium is by molten salt electrolysis while potassium is elevated temperatures between 1075 1C and 1100 1C. produced using sodium in a metallothermic reduction This process changes the naturally occurring alpha- process. Lithium cell uses a salt mixture of lithium spodumene into beta-spodumene, which can be more chloride and potassium chloride whereas sodium cell readily attacked by the acid. The beta-spodumene is (Downs cell) uses a mixture of sodium chloride and further cooled and ball-milled. This powder is then calcium chloride. The occurrence, metallurgical ex- roasted in a second kiln under an excess of sulfuric traction methods, chemical properties, and prominent acid at a temperature between 200 1C and 250 1C. The applications, including those of the compounds of following reaction occurs at this stage: alkali metals—lithium, sodium, and potassium—have been described. Alkali metals are excellent reductants for other metal compounds, since alkali metals form Li2OÁAl2O3Á4SiO2 þ H2SO4 some of the most stable compounds. Thus, a hybrid -H2OÁAl2O3Á4SiO2 þ Li2SO4 at 2002250 1C ð1Þ process has been outlined where the alkali metal is electrochemically produced and used as a pyrochem- Once this reaction has taken place, the kiln is then ical reductant in situ. In this scheme, alkali metal leached with water. This yields a lithium sulfate serves as a nonconsumable reducing metal. product to be treated with sodium carbonate to convert it into lithium carbonate. Hydrochloric acid can then be used to react with the lithium carbonate to 2. Lithium form lithium chloride. 2.1 Sources of Lithium Li2SO4 þ Na2CO3-Li2CO3 þ Na2SO4 ð2Þ Lithium in nature, is primarily obtained from lithium-bearing pegmatites and brines. The lithium Li2CO3 þ 2HCl-2LiCl þ H2CO3 ð3Þ found within the pegmatite formations is in the mineral forms of spodumene, petalite, lepidolite, and In the alkaline cleaning process, either a spodumene amblygonite. These pegmatites are found as veins or a lepidolite concentrated ore is ground and calcined within or associated with granites and feldspar and with a mixture of 3.5 parts limestone to 1 part lithium. are generally the primary sources for extraction This is done at a temperature between 900 1Cand of lithium. The mineral, spodumene (Li2OÁAl2O3Á 1000 1C. In this process, the kiln is then hot-leached 4SiO2), is of primary interest for the commercial with water and the product is lithium hydroxide, production of lithium in North America due to its which can be converted to lithium chloride using 1 Alkali Metals Production (Li, Na, K) hydrochloric acid: cathode with cast iron collectors and a graphite anode is employed. Tables 1 and 2 show that lithium has a Li 2OÁAl2O3Á4SiO2 þ CaO lower density than the electrolytes. Therefore, the metal floats on top. The collector is helpful in the -CaOÁAl2O3Á4SiO2 þ Li2Oat90021000 1C ð4Þ recovery of the metal. The electrical and ionic conductivities in the cell and the fluidity of the Li O þ H O þ 2HCl-2LiCl þ 2H O ð5Þ electrolyte, are critical parameters that control the 2 2 2 material and energy balance of the process. Electrolytic lithium is refined by remelting, when Lithium chloride is thus the source for electrolytic the insolubles either float to the surface or sink extraction of lithium. Metallic lithium can be obtained to the bottom of the melt pot. Potassium is only by the electrolysis of a melt, comprising of an equal slightly miscible in lithium. The remelting step mixture of lithium chloride and potassium chloride. A produces lithium metal with less than 100 ppm of schematic diagram of this cell can be seen in Fig. 1 potassium. (Freitas 2000). Lithium chloride is fed into the cell, which is operated at a temperature between 400 1C and 420 1C. The voltage across the cell of molten 2.3 Applications of Lithium lithium chloride and potassium chloride, is typically between 8 V and 9 V with a current consumption of Table 1 lists some of the physicochemical properties 40 kWh kgÀ1 of lithium that is produced. A steel of the alkali metals. Its low density makes it a very useful alloying agent. The major industrial use of lithium is for lubricating greases in the form of lithium stearate. Lithium-based greases provide high temperature and water resistance as well as having good low temperature properties. A relatively new, but very popular application of lithium is for lightweight alkaline batteries in which the anode is comprised of lithium. Metallic lithium is also added to certain types of glasses and ceramics, as a flux to lower melting and sintering temperatures, as well as to lower the coefficient of expansion in the finished product (Fishwick 1974). Lithium can also be added to electrolytic cells in the production of aluminum to increase yield and reduce fluorine. Lithium also finds many uses in inorganic compounds, particularly in the form of chlorides and fluorides. Table 3 lists the prominent applications (Roskill 1979). 3. Sodium 3.1 Sources of Sodium Figure 1 Illustration of a cell for electrolytic production of As one of the most abundant minerals on earth, lithium (Freitas 2000). sodium is most commonly derived from natural salts. Table 1 Physicochemical properties of lithium, sodium, and potassium. Properties Lithium Sodium Potassium At. weight (At. no) 6.94 (3) 22.98 (11) 39.1 (19) Melting point, 1C 180.5 97.8 63.7 Boiling point, 1C 1336 892 760 Density, g cmÀ3 0.53 0.97 0.86 Thermal conductivity, cal/(s.cm.1C) 0.17 0.334 0.107 Specific heat (250 1C), cal gÀ1 0.849 0.295 0.177 Heat of fusion, cal gÀ1 103.2 27.05 14.6 Electronegativity, Pauling’s 1.0 0.9 0.8 Atomic volume, W/D 13.1 23.7 45.3 2 Alkali Metals Production (Li, Na, K) Table 2 Physicochemical properties of relevant metal chlorides. Properties LiCl NaCl KCl CaCl2 Melting point, 1C 610 800.7 771 775 Boiling point, 1C 1383 1465 1500 (sub) 1935 Density, g cmÀ3 2.068 2.17 1.988 2.15 Mol. wt. 42.4 58.5 74.6 111 Std. free energy of formation (25 1C), kJ molÀ1 À384.4 À384.1 À408.5 À748.8 Std. dissociation potential, V 3.98 3.98 4.23 3.88 Elec. conductivity, OÀ1cmÀ1 5.814 3.657 2.303 Table 3 Applications of lithium compounds. Compound Application Lithium acetate Organic synthesis. Lithium aluminate Flux in highly refractory porcelain enamels. Lithium aluminum Preparation of vitamins, steroids, and Ziegler catalysts. Solvent drying and generation hydride of hydrogen. Lithium tetraborate Ceramics. Lithium bromide Reconstitution of brines, catalyst and dehydro-halogenating agent, swelling agent for proteins. Lithium carbonate Enamels, glasses, glazes, and ceramic specialties. Extractive metallurgy of aluminum and uranium. Pharmaceutical. Lithium chloride Preparation of lithium metal, brazing fluxes, electrolytes of low-temperature dry cell batteries, fire extinguishing solutions. Lithium chromate brine Corrosion inhibitor for lithium chloride and bromide brines, industrial battery additive, paint remover. Lithium fluoride Strong flux for enamels, glasses and glazes, welding and brazing fluxes, electrowinning of aluminum, heat sink material. Lithium hydride Amide and double hydrides of lithium, catalyst in polymerization reactions, hydrogen generation, radiation shielding, high energy fuels, fuel cells, heat sink, silane gas production. Lithium hydroxide Multi-purpose lubricating greases, additive to the KOH electrolyte of alkaline batteries, anhydrous lithium hydroxide used as a CO2 absorbent in air purification systems of submarines and space capsules, alkaline reagent for corrosion inhibition in steam boilers, component of copper electroplating baths, absorption of CO2 in air conditioning systems.
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