Lithium major producers

The thermochemistry of 4,4-diphenylcyclohexa-2,5-dienylidene (lu) in solution was investigated by Freeman and Pugh (Scheme 19).106 The thermal decomposition of the diazo compound 2u (produced in situ from the corresponding tosylhydrazone lithium salt) produces a complex product mixture with the azine as the major product (51%). Volatile monomeric products biphenyl and several terphenyls were also formed in low yields. 

In 2008, the world s largest consumer of lithium minerals and compounds was the United States. The major producer of lithium chemicals worldwide was Chile. Other countries involved in lithium production included Argentina, Australia, Brazil, Canada, China, Portugal, the United States, and Zimbabwe. Specific information on U.S. production was not released in order to preserve trade secrets. 

Lithium-ion batteries are the most popular rechargeable batteries—from zero market share in the battery market, in 1990, to a clear leadership in the current world sales [1]. Especially in the past decade, the production of lithium batteries has increased very fast [2]. Data of City Research for 2011 show that Japan and Korea are the major producers (both with 39%), while China is third with 14%. Other companies in North America and Europe have 8% of the global market [3]. The highest shares in the 2011 market were for Panasonic/Sanyo and Samsung SDI, each having 24% of the market LG Chemical and Sony followed with 16% and 8%, respectively. Other companies have shares below 5% [3]. Figure 23.1 presents selected manufacturers of components, cells and battery systems. As can be noticed, the majority of companies have headquarters in Asia. 

Table 4.3. Major producers of lithium mineral concentrates (2002)...

Table 4.6 summarizes the major lithium-carbonate producers and suppliers. Close examination indicates that SQM s lithium-rich brine operation is now the largest lithium-carbonate operation in the world. In addition to lithium carbonate, the Minsal facility has the capacity to produce annually 300,000 tonnes of potash, which it uses at its local fertilizer operation, 250,000 tonnes of potassium chloride, and 16,000 tonnes of boric acid and, to a lesser extent, iodine. 

Table 4.6. Major producers of lithium carbonate Company...

According to a report by Roskill Information Services published in 2003, the lithium market is characterized by a high degree of consolidation. Actually, three major producers—Sons of Gwalia in Australia, Tanco in Canada, and Bikita Minerals in Zimbabwe—represent the major lithium mineral producers, while Sociedad Quimica y Minera de Chile SA (SQM) and Sociedad Chilena de Litio (SCL) control the world s supply of lithium carbonate, and Chemetall GmbH of Germany and FMC Corp. of the USA dominate the manufacture of lithium metal and hthium chemicals. 

The Battery Association of Japan provides detailed information on Japanese production of hthium-ion cells (http //wuw.haj.or.jp/e/), which has increased steadily since 2001 to over 1.2 bilHon cells in 2008 (see Figure 20.1). Major producers of hthium-ion ceUs for consumer apphcations include Samsung, Sanyo, Matsushita, Sony, LG Chem, BYD, and lishen. Many of these companies are also entering the automotive market for hthium-ion ceUs, which is at present smaU. lithium-ion ceUs faU into three types cylindrical, prismatic, and pouch. Cylindrical and prismatic ceUs are usually contained in metal cans (aluminum or nickel-plated steel) and the electrodes are typicaUy spiraUy wound. However, stacks are sometimes used in prismatic cells as are plastic cases. Pouch ceUs use a laminate material, typicaUy nylon/aluminum/polypropylene (PP) as the packaging material. The electrodes in pouch ceUs can be spirally wound or stacked. 

Mali Energy Ltd (US) are a major producer of lithium-molybdenum disulphide batteries. They... 

The recovery of lithium from spodumene ore was discontinued by Foote in 1984 (1986, USGS, 2000) and the mine and plant placed in a stand-by condition. It was officially closed in 1991 and the mine and plant dismantled in 1994 (USGS, 1997). However, the Kings Mountain conversion plant (converting lithium hydroxide to other lithium products) continued as a major processor of Clayton Valley and Salar de Atacama lithium carbonate into other lithium chemicals and lithium metal. Butyl lithium was produced at their New Johnsonville, Tennessee and Taiwan plants, and many other lithium chemicals were made at their parent company, Chemetall GmbH s plant at Langelsheim, Germany. 

Some industrial processes produce predorninately latent air conditioning loads. Others dictate very low humidities and when the dew point falls below 0°C, free2ing becomes a major concern. Dehydration equipment, using soHd sorbents such as siUca gel and activated alurnina, or Hquid sorbents such as lithium chloride brine and triethylene glycol, may be used. The process is exothermic and may require cooling the exiting air stream to meet space requirements. Heat is also required for reactivation of the sorbent material. 

Transmetalation of lithium enolate 1 a (M = Li ) by treatment with tin(II) chloride at — 42 °C generates the tin enolate that reacts with prostereogenic aldehydes at — 78 °C to preferentially produce the opposite aldol diastereomer 3. Diastereoselectivities of this process may be as high as 97 3. This reaction appears to require less exacting conditions since similar results are obtained if one or two equivalents of tin(ll) chloride arc used. The somewhat less reactive tin enolate requires a temperature of —42 C for the reaction to proceed at an acceptable rate. The steric requirements of the tin chloride counterion are probably less than those of the diethyla-luminum ion (vide supra), which has led to the suggestion26 44 that the chair-like transition state I is preferentially adopted26 44. This is consistent with the observed diastereoselective production of aldol product 3, which is of opposite configuration at the / -carbon to the major product obtained from aluminum enolates. 

This high diastereoselectivity contrasts dramatically with the nearly nonexistent selectivity of the lithium enolate of the corresponding triphenylphosphane complexes (vide supra). The diastereomer preferentially obtained from the fluorophenyl lithium enolate 9 corresponds to the major product produced by reaction of the aluminum enolate 1 b derived from the parent triphenylphosphane complex. 

The diastereoselectivity of this reaction contrasts dramatically with the generally low selectiv-ities observed for aldol reactions of lithium enolates of iron acyls. It has been suggested thal this enolate exists as a chelated species48 the major diastereomer produced is consistent with the transition state E which embodies the usual antiperiplanar enolate geometry. 

Enantiomerically pure /J-keto sulfoxides are prepared easily via condensation of a-lithiosulfinyl carbanions with esters. Reduction of the carbonyl group in such /J-keto sulfoxides leads to diastereomeric /J-hydroxysulfoxides. The major recent advance in this area has been the discovery that non-chelating hydride donors (e.g., diisobutylaluminium hydride, DIBAL) tend to form one /J-hydroxysulfoxide while chelating hydride donors [e.g., lithium aluminium hydride (LAH), or DIBAL in the presence of divalent zinc ions] tend to produce the diastereomeric /J-hydroxysulfoxide. The level of diastereoselectivity is often very high. For example, enantiomerically pure /J-ketosulfoxide 32 is reduced by LAH in diethyl ether to give mainly the (RR)-diastereomer whereas DIBAL produces exclusively the (.S R)-diastereomer (equation 30)53-69. A second example is shown in... 

In the highly competitive arena surrounding the Pfizer compounds CP-263,114 and CP-225,917 (Figure 4.2), Nicolaou and co-workers employed a hydrozirconation—iodination sequence to produce vinyl iodide 4 [17]. Lithium—halogen exchange and subsequent conversion to enone 5 sets the stage for a Lewis acid assisted intramolecular Diels—Alder reaction affording polycyclic 6 as the major diastereomer (Scheme 4.3). 

Reduction of dibenzothiophene with sodium in liquid ammonia has been shown to be sensitive to the experimental methods employed however, the major product is usually 1,4-dihydrodibenzothiophene. 27 -28i The electrochemical reduction of dibenzothiophene in ethylene-diamine-lithium chloride solution has been shown to proceed via stepwise reduction of the aromatic nucleus followed by sulfur elimination. In contrast to the reduction of dibenzothiophene with sodium in liquid ammonia, lithium in ethylenediamine, or calcium hexamine in ether, electrolytic reduction produced no detectable thiophenol intermediates. Reduction of dibenzothiophene with calcium hexamine furnished o-cyclohexylthiophenol as the major product (77%). Polaro-graphic reduction of dibenzothiophene 5,5-dioxide has shown a four-electron transfer to occur corresponding to reduction of the sulfone group and a further site. ... 

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