Lithium manufacturing

Rubidium, Cesium Rubidium and cesium, the two most chemically reactive of the common alkali metals, were both detected as impurities in other substances by chance observation of their characteristic colored spectral lines (Section 5.3). Rubidium, named from the Latin rubidius (deepest red), occurs as an impurity in the mineral lepidolite, l LisAlsSigC OFLF) and is obtained as a byproduct of lithium manufacture. Cesium, named from the Latin caesius (sky blue), also occurs with lithium in many minerals and is found in pollucite (Cs4Al4Si9026-H20). Neither rubidium nor cesium has any major commercial importance. 

To build up the polyene chains, the (E/Z)- isomers of the C6-unit 19 are produced from the ketone 20 and acetylene (4) in three steps (Scheme 3). Lithium amide is first reacted with acetylene (4) in liquid ammonia and the solvent is then replaced by an ether. The lithium acetylide-ammonia complex 21 thus formed yields, after 1,2-addition to 20 and aqueous work-up, the tertiary carbinol 22. Excess ammonia and acetylene (4) are largely recycled back into the process. The lithium manufacturer can recycle the recovered and prepurified aqueous lithium hydroxide solution. The entire process was optimized with respect to reaction conditions in the 1980s and may be regarded as a model process from the environmental and economic points of view [17]. 

Manufacture. Lithium fluoride is manufactured by the reaction of lithium carbonate or lithium hydroxide with dilute hydrofluoric acid. If the lithium carbonate is converted to the soluble bicarbonate, insolubles can be removed by filtration and a purer lithium fluoride can be made on addition of hydrofluoric acid (12). High purity material can also be made from other soluble lithium salts such as the chloride or nitrate with hydrofluoric acid or ammonium bifluoride (13). 

Although a few simple hydrides were known before the twentieth century, the field of hydride chemistry did not become active until around the time of World War II. Commerce in hydrides began in 1937 when Metal Hydrides Inc. used calcium hydride [7789-78-8J, CaH2, to produce transition-metal powders. After World War II, lithium aluminum hydride [16853-85-3] LiAlH, and sodium borohydride [16940-66-2] NaBH, gained rapid acceptance in organic synthesis. Commercial appHcations of hydrides have continued to grow, such that hydrides have become important industrial chemicals manufactured and used on a large scale. 

Preparation. Commercial manufacture of LiAlH uses the original synthetic method (44), ie, addition of a diethyl ether solution of aluminum chloride to a slurry of lithium hydride (Fig. 2). 

Flint clays and other related rocks are another potential lithium source. These are high alumina clays that are composed largely of we11-crysta11i2ed kaolinite [1318-74-1] and are used for the manufacture of refractories (qv). The lithium content ranges from <100 to 5000 ppm. Deposits occur in many states, including Missouri, Peimsylvania, and Ohio. Lithium (at ca 1.3%) is present in a chlorite mineral that is similar to cookeite [1302-92-7]. High lithium contents may be the reason why some deposits are unsatisfactory for refractory use. 

Uses. The largest use of lithium metal is in the production of organometaUic alkyl and aryl lithium compounds by reactions of lithium dispersions with the corresponding organohaHdes. Lithium metal is also used in organic syntheses for preparations of alkoxides and organosilanes, as weU as for reductions. Other uses for the metal include fabricated lithium battery components and manufacture of lithium alloys. It is also used for production of lithium hydride and lithium nitride. 

Commercial lithium peroxide has been assigned UN No. 1472 and should be transported in accordance with international transport regulations pertaining to Class 5.1, oxidizing substances. It is manufactured by ChemetaH AG (Germany) and Lithium Corp. of America (United States). The U.K. price in 1994 was J48—198/kg ( 70—285/kg), depending on quantity. 

In this process, the fine powder of lithium phosphate used as catalyst is dispersed, and propylene oxide is fed at 300°C to the reactor, and the product, ahyl alcohol, together with unreacted propylene oxide is removed by distihation (25). By-products such as acetone and propionaldehyde, which are isomers of propylene oxide, are formed, but the conversion of propylene oxide is 40% and the selectivity to ahyl alcohol reaches more than 90% (25). However, ahyl alcohol obtained by this process contains approximately 0.6% of propanol. Until 1984, ah ahyl alcohol manufacturers were using this process. Since 1985 Showa Denko K.K. has produced ahyl alcohol industriahy by a new process which they developed (6,7). This process, which was developed partiy for the purpose of producing epichlorohydrin via ahyl alcohol as the intermediate, has the potential to be the main process for production of ahyl alcohol. The reaction scheme is as fohows ... 

Potassium siUcates are manufactured in a manner similar to sodium siUcates by the reaction of K CO and sand. However, crystalline products are not manufactured and the glass is suppHed as a flake. A 3.90 mole ratio potassium siUcate flake glass dissolves readily in water at ca 88°C without pressure by incremental addition of glass to water. The exothermic heat of dissolution causes the temperature of the solution to rise to the boiling point. Lithium sihcate solutions are usually prepared by dissolving siUca gel in a LiOH solution or mixing colloidal siUca with LiOH. 

As of this writing, there is Httle commercialization of advanced battery systems. Small rechargeable lithium button cells have been commercialized, however, by Sanyo, Matsushita (Panasonic), and Toshiba. These cells are intended for original equipment manufacturer (OEM) use in appHcations such as memory backup and are not available to the general consumer. 

Boron Triiodide. There are no large-scale commercial uses of boron ttiiodide. It can cleave ethers without affecting aldehyde groups and thus finds use in the synthesis of the antibiotic fmstulosin (115,116). BI is used to prepare Snl, Sbl, and Til (117) in 99—100% yield. It is used to clean equipment for handling UE (118) and in the manufacture of lithium batteries (119). 

Calcium hypochlorite is the principal commercial soHd hypochlorite it is produced on a large scale and marketed as a 65—70% product containing sodium chloride and water as the main diluents. A product with a significantly higher available chlorine, av CI2, (75—80%) has been introduced by Olin. Calcium hypochlorite is also manufactured to a smaller extent as a hemibasic compound (- 60% av Cl ) and to a lesser extent in the form of bleaching powder (- 35% av CI2). Lithium hypochlorite is produced on a small scale and is sold as a 35% assay product for specialty appHcations. Small amounts of NaOCl ate employed in the manufacture of crystalline chlorinated ttisodium phosphate [56802-99-4]. 

Manufacture. Calcined spodumene [1302-37-0], a lithium aluminum sihcate, LiAlSi O, is treated with sulfuric acid, neutralized to pH 6, and... 

Many random copolymers have found commercial use as elastomers and plastics. For example, SBR (62), poly(butadiene- (9-styrene) [9003-55-8] has become the largest volume synthetic mbber. It can be prepared ia emulsion by use of free-radical initiators, such as K2S20g or Fe /ROOH (eq. 18), or in solution by use of alkyl lithium initiators. Emulsion SBR copolymers are produced under trade names by such companies as American Synthetic Rubber (ASPC), Armtek, B. F. Goodrich (Ameripool), and Goodyear (PHoflex) solution SBR is manufactured by Firestone (Stereon). The total U.S. production of SBR in 1990 was 581,000 t (63). 

Most commercial liquid ammonia contains up to several ppm of colloidal iron compounds, possibly the iron oxide catalyst commonly used in manufacturing ammonia. Reduction converts these compounds to colloidal iron which strongly catalyzes the reaction between alcohols and sodium and potassium. The reaction of lithium with alcohols is also catalyzed by iron but to a markedly lesser degree. The data in Table 1-4 illustrate the magnitude of these catalytic effects. The data of Table 1-5 emphasize how less than 1 ppm... 

In summary, methanol as a mobile-phase modifier has a significant effect on the separation of PVP in aqueous SEC with these four linear columns. The best separation of all PVP grades can be achieved with the SB-806M column in 50 50 water/methanol with 0.1 M lithium nitrate. It is interesting to note that despite the improvements reported by the manufacturers for the newer columns (SB-806MHQ and PWxl), the newer columns do not necessarily perform better than the older columns (SB-806 and PW) for aqueous SEC of PVP. 

---