Lithium extraction

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. 

Americium and other actinide elements may be separated from lanthanides by solvent extraction. Lithium chloride solution and an eight to nine carbon tertiary amine are used in the process. Americium is then separated from curium by the above methods. 

C. Extraction. Lithium occurs in the form of several minerals and in brines and brine deposits. A brine is water with sizable concentrations of halide salts. 

Lithium.—In order to extract lithium from the silicate minerals—petalite, lepidolite, spodumene, amblygonite, etc.—J. J. Berzelius 3 fused the finely powdered mineral with twice its weight of calcium or barium carbonate. L. Troost fused a mixture of finely powdered lepidolite with an equal weight of barium carbonate, half its weight of barium sulphate, and one-third its weight of potassium sulphate. In the latter case, two layers were formed lithium and potassium sulphates accumulated in the upper layer from which they were extracted by simple lixiviation. The sulphates are converted to chlorides by treatment with barium chloride. The filtered liquid is evaporated to dryness, and the chlorides extracted with a mixture of absolute alcohol, or pyridine. The lithium chloride dissolves, the other alkali chlorides remain as an almost insoluble residue. 

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Given and coworkers studying the "British Macerals" took more of an organic chemist s approach to characterization. The macerals were subjected to solvent extraction, lithium reduction, hydroxyl determination, oxidation, and reaction with various reagents. N-bromosuccinimide (NBS) was used to bromin-ate aliphatic carbons which in the case for four macerals from an Aldwarke Silkstone coal yielded per 100 carbon atoms the following distribution of hydrogen which is replaced by bromine (61) vitrinite 16, exinite 25 1/2, micrinite 12, and fusinite... 

FIGURE 14.7. Effect of the addition of alcohol on the lithium ion leakage from DOLPA reverse micelles during back extraction. A back-extraction operation was performed by contacting the reverse micellar solution extracting lithium in advance and the fresh recovery of the aqueous solution. The observed amounts of lithium ion in each phase were measured using an ICP analyser. 

Double compounds of lithium and aluminium are used to extract lithium from aqueous salt-containing solutions [3]. They decompose in water releasing lithium compounds. 

Extraction methods in lithium recovery processes have not found as wide use as other techniques. When several extractants, such as C3-C primary alcohols and Cg-Cg aliphatic ketones were tried for this purpose, isobutanol, the one that seemed to be the most promising yielded separation coefficient values for Li and Mg, and Na and K that were too low. Separation factors were increased by extracting lithium complexes with chlorides of iron, nickel, or cobalt in acidic media [126]. The most... 

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). 

The reaction between spodumene or lepidolite and quicklime is also used to some extent for extracting lithium in the form of lithium hydroxide (LiOH) from ores... 

The use of LMO in batteries was first reported by Hunter in 1982, who prepared X-MnO by extracting lithium from LMO and applied it as a cathode-active material for lithium primary batteries. Application of LMO to a lithium secondary battery was first reported by Thackeray et al. in 1984. ... 

Sources of potentially extractable lithium can generally be divided into brines (salt flats, geothermal brines and oil field brines), minerals, clays and oceans. There is a variety of reserve and resource estimates by different institutions or in various publications... 

LiVOj is isostructural with LiCoO it has a da ratio of 5.20 (space group R3m ) [74]. Unlike LiCoO, and LiNiOj, LiVOj is unstable to delithiation at x 0.3 inLi,, .V02, the vanadium ions become mobile and diffuse from the octahedral sites (3b) of the vanadium layer into octahedral sites (3a) left vacant by the extracted lithium ions. The diffusion of vanadium ions takes place through face-shared tetrahedra linking the octahedra of alternate layers and is believed to occur by a disproportionation reaction in which ions occupy tetrahedral (6c) sites [74, 751 ... 

The disordered aluminium hydroxide and the chloride of the double hydroxide of lithium and aluminium (LADH-Cl) synthesized on the basis of the former species are capable of extraction lithium selectively from complex salt chloride systems while the well crystalline compounds possess these properties to a lesser extent. The formation of LADH-Cl from aluminium hydroxide, desorption and sorption of lithium chloride are connected with the processes of its intercalation-deintercalation in the layered matrix. These processes can be described by the following scheme ... 

One of the most important methods of testing of the EASPs is their gatvano-static reduction and oxidation. The analogous method in electroanalytical chemistry is called chronopotentiometry (CPM). In CPM, the transient time corresponds to the utilization of the battery electrode. The transient time is the time when the surface concentration of the depolarizer drops to zero the utilization is the fraction of inserted (extracted) lithium atoms. Obviously, at constant current conditions the difference between these characteristics is solely a matter of units. However, since the guest s concentration varies from (sometimes) zero to a certain maximal value, the DC will suffer aU possible variations as weU, and aU the CPM equations cannot be used, except the single CPM relationship given below. 

Many other organic compounds have been noted that might be able to somewhat selectively extract lithium, but essentially all of them also extract magnesium, and require a drastic pH or composition modification of the brine. For instance some... 

Armstrong AR, Robertson AD, Bruce PG (2005) Overcharging manganese oxides extracting lithium beyond Mn". J Power Sourc 146 275-280... 

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