Rare earths Extraction

The air concentrations of thorium and other airborne radioactivity near a former thorium and rare-earth extraction facility in the United States were measured. The maximum radioactivity due to all three isotopes of thorium at a site about 450 feet from the primary waste pile was 0.66 fCi/m. Although the background thorium radioactivity was not reported, the total radioactivity at a site about 4000 feet south of the waste pile was about 3.5 times lower than a site 450 feet from the pile (Jensen et al. 1984). 

Presently. 24 isotopes of actinium, with mass numbers ranging from 207 to 2.30, have been identified. All are radioactive. One year after the discovery of polonium and radinm by the Curies, A. Debierne found an unidentified radioactive substance in the residue after treatment of pitchblende. Debierne named the new material actinium after the Greek word for ray. F. Giesel, independently in 1902, also found a radioactive material in the rare-earth extracts of pitchblende. He named... 

The current operator of the mine is Steenkampskraal Monazite Mine (Pty) Ltd. (SMM), which is 75 % owned by Rare Earth Extraction Company ( Rareco ). This company is fully owned by the Great Western Minerals Group. 

Following a brief summary of rare earth extraction and liquid-liquid extraction of actinides using molecular solvents, the author reviews and discusses the main properties of ionic liquids that are of importance to liquid-liquid extraction. The various ways in which ionic liquids are used for the extraction/separation of rare earths and actinides either as replacement solvents or as simple additives are then critically reviewed. The focus of the chapter is on the mechanisms of extraction in ionic liquids, and the differences between ionic liquids and molecular solvents are highlighted. 

Uranium extraction Rare earth extraction Cobalt/nickel separation Zinc extraction, etc. 

Desalination Division and Uranium and Rare Earths Extraction Division, Bhabha Atomic Research Centre, Bombay 400085, India... 

The solvent extraction reaction chemistry in specific medium, extractants, pH, diluents, and in synergistic systems are discussed in relation to the transfer of the rare earth extractable complex from the aqueous phase to the organic phase. 

Bauer and Lindstrom (1964) reported moderate success in the use of naphthenic acid as an extractant for rare earth sulfates with diethylether or n-hexanol as a diluent. The extraction required 6 mols of naphthenic acid to 1 mol of rare earth oxide at pH ra 7.6. Rare earth extraction was dependent on pH, naphthenic acid concentration, and the mol ratio of naphthenic acid to rare earth. 

Bautista, R.G., and M.M. Wong, 1989, Rare Earths, Extraction, Preparation and Applications (TMS, Warrendale, PA). 

Keywords Ionic liquids Rare earth Extraction Separation Metal recycling... 

Lanthanum was isolated in relatively pure form in 1923. Iron exchange and solvent extraction techniques have led to much easier isolation of the so-called "rare-earth" elements. 

Gr. prasios, green, and didymos, twin) In 1841 Mosander extracted the rare earth didymia from lanthana in 1879, Lecoq de Boisbaudran isolated a new earth, samaria, from didymia obtained from the mineral samarskite. Six years later, in 1885, von Welsbach separated didymia into two others, praseodymia and neodymia, which gave salts of different colors. As with other rare earths, compounds of these elements in solution have distinctive sharp spectral absorption bands or lines, some of which are only a few Angstroms wide. 

Gr. neos, new, and didymos, twin) In 1841, Mosander, extracted from cerite a new rose-colored oxide, which he believed contained a new element. He named the element didymium, as it was an inseparable twin brother of lanthanum. In 1885 von Welsbach separated didymium into two new elemental components, neodymia and praseodymia, by repeated fractionation of ammonium didymium nitrate. While the free metal is in misch metal, long known and used as a pyrophoric alloy for light flints, the element was not isolated in relatively pure form until 1925. Neodymium is present in misch metal to the extent of about 18%. It is present in the minerals monazite and bastnasite, which are principal sources of rare-earth metals. 

The element may be obtained by separating neodymium salts from other rare earths by ion-exchange or solvent extraction techniques, and by reducing anhydrous halides such as NdFs with calcium metal. Other separation techniques are possible. 

Gadolinium is found in several other minerals, including monazite and bastnasite, both of which are commercially important. With the development of ion-exchange and solvent extraction techniques, the availability and prices of gadolinium and the other rare-earth metals have greatly improved. The metal can be prepared by the reduction of the anhydrous fluoride with metallic calcium. 

Ytterbium occurs along with other rare earths in a number of rare minerals. It is commercially recovered principally from monazite sand, which contains about 0.03%. Ion-exchange and solvent extraction techniques developed in recent years have greatly simplified the separation of the rare earths from one another. 

Other Metals. Because of the large number of chemical extractants available, virtually any metal can be extracted from its aqueous solution. In many cases extraction has been developed to form part of a viable process (275). A review of more recent developments in metal extraction including those for precious metals and rare earths is also available (262). In China a complex extraction process employing a cascade of 600 mixer—settlers has been developed to treat leach Hquor containing a mixture of rare earths (131). 

The lanthanides form many compounds with organic ligands. Some of these compounds ate water-soluble, others oil-soluble. Water-soluble compounds have been used extensively for rare-earth separation by ion exchange (qv), for example, complexes form with citric acid, ethylenediaminetetraacetic acid (EDTA), and hydroxyethylethylenediaminetriacetic acid (HEEDTA) (see Chelating agents). The complex formation is pH-dependent. Oil-soluble compounds ate used extensively in the industrial separation of rate earths by tiquid—tiquid extraction. The preferred extractants ate catboxyhc acids, otganophosphoms acids and esters, and tetraaLkylammonium salts. 

Separation Processes. The product of ore digestion contains the rare earths in the same ratio as that in which they were originally present in the ore, with few exceptions, because of the similarity in chemical properties. The various processes for separating individual rare earth from naturally occurring rare-earth mixtures essentially utilize small differences in acidity resulting from the decrease in ionic radius from lanthanum to lutetium. The acidity differences influence the solubiUties of salts, the hydrolysis of cations, and the formation of complex species so as to allow separation by fractional crystallization, fractional precipitation, ion exchange, and solvent extraction. In addition, the existence of tetravalent and divalent species for cerium and europium, respectively, is useful because the chemical behavior of these ions is markedly different from that of the trivalent species. 

Liquid—Liquid Extraction. The tiquid—tiquid extraction process for the rare-earth separation was discovered by Fischer (14). Extraction of REE using an alcohol, ether, or ketone gives separation factors of up to 1.5. The selectivity of the distribution of two rare-earth elements, REI and RE2, between two nonmiscible tiquid phases is given by the ratio of the distribution coefficients DI and D2 ... 

Another characteristic of the solvent extraction system is the high solute concentration in both aqueous and organic phases, which influences greatly the size of the required installation. Concentrations of rare-earth oxides (REO) higher than 100 g/L are often reached in both phases. The process therefore requires only relatively small equipment. 

Table 7. Commercial Extractants Available for Rare-Earth Separation...

The extent of extraction can be increased by a salting out effect. The selectivity of TBP is very poor compared with HDEHP and it is only useful for light rare-earth separation however, organic phase loadings or REO higher than 100 g/L can easily be achieved. There are a large number of TBP manufacturers in Japan, the United States, and Europe. 

Equipment. The preferred extraction technique in the rare-earth industry uses mixer—setders. There are two basic reasons. The first is the use of relatively... 

Extraction of Bertrandite. Bertrandite-containing tuff from the Spor Mountain deposits is wet milled to provide a thixotropic, pumpable slurry of below 840 p.m (—20 mesh) particles. This slurry is leached with sulfuric acid at temperatures near the boiling point. The resulting beryUium sulfate [13510-49-1] solution is separated from unreacted soflds by countercurrent decantation thickener operations. The solution contains 0.4—0.7 g/L Be, 4.7 g/L Al, 3—5 g/L Mg, and 1.5 g/L Fe, plus minor impurities including uranium [7440-61-1/, rare earths, zirconium [7440-67-7] titanium [7440-32-6] and zinc [7440-66-6]. Water conservation practices are essential in semiarid Utah, so the wash water introduced in the countercurrent decantation separation of beryUium solutions from soflds is utilized in the wet milling operation. 

The same color variety is not typical with inorganic insertion/extraction materials blue is a common transmitted color. However, rare-earth diphthalocyanine complexes have been discussed, and these exhibit a wide variety of colors as a function of potential (73—75). Lutetium diphthalocyanine [12369-74-3] has been studied the most. It is an ion-insertion/extraction material that does not fit into any one of the groups herein but has been classed with the organics in reviews. Films of this complex, and also erbium diphthalocyanine [11060-87-0] have been prepared successfiiUy by vacuum sublimation and even embodied in soHd-state cells (76,77). 

Harrowfield et al. [37-39] have described the structures of several dimethyl sulfoxide adducts of homo bimetallic complexes of rare earth metal cations with p-/e rt-butyl calix[8]arene and i /i-ferrocene derivatives of bridged calix[4]arenes. Ludwing et al. [40] described the solvent extraction behavior of three calixarene-type cyclophanes toward trivalent lanthanides La (Ln = La, Nd, Eu, Er, and Yb). By using p-tert-huty ca-lix[6Jarene hexacarboxylic acid, the lanthanides were extracted from the aqueous phase at pH 2-3.5. The ex-tractability is Nb, Eu > La > Er > Yb. 

A freshly manufactured zeolite has a relatively high UCS in the range of 24.50°A to 24.75°A. The thermal and hydrothermal environment of the regenerator extracts alumina from the zeolite structure and, therefore, reduces its UCS. The final UCS level depends on the rare earth and sodium level of the zeolite. The lower the sodium and rare earth content of the fresh zeolite, the lower UCS of the equilibrium catalyst (E-cat). 

---