Lanthanide , solvent extraction

Yttrium and lanthanum are both obtained from lanthanide minerals and the method of extraction depends on the particular mineral involved. Digestions with hydrochloric acid, sulfuric acid, or caustic soda are all used to extract the mixture of metal salts. Prior to the Second World War the separation of these mixtures was effected by fractional crystallizations, sometimes numbered in their thousands. However, during the period 1940-45 the main interest in separating these elements was in order to purify and characterize them more fully. The realization that they are also major constituents of the products of nuclear fission effected a dramatic sharpening of interest in the USA. As a result, ion-exchange techniques were developed and, together with selective complexation and solvent extraction, these have now completely supplanted the older methods of separation (p. 1228). In cases where the free metals are required, reduction of the trifluorides with metallic calcium can be used. 

The separation of basic precipitates of hydrous Th02 from the lanthanides in monazite sands has been outlined in Fig. 30.1 (p. 1230). These precipitates may then be dissolved in nitric acid and the thorium extracted into tributyl phosphate, (Bu"0)3PO, diluted with kerosene. In the case of Canadian production, the uranium ores are leached with sulfuric acid and the anionic sulfato complex of U preferentially absorbed onto an anion exchange resin. The Th is separated from Fe, A1 and other metals in the liquor by solvent extraction. 

Because of the technical importance of solvent extraction, ion-exchange and precipitation processes for the actinides, a major part of their coordination chemistry has been concerned with aqueous solutions, particularly that involving uranium. It is, however, evident that the actinides as a whole have a much stronger tendency to form complexes than the lanthanides and, as a result of the wider range of available oxidation states, their coordination chemistry is more varied. 

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. 

The application of these methods is described in some detail for recovery of base metals and platinum group metals in Sections 9.17.5-9.17.6 focusing mainly on solution-based hydrometal-lurgical operations, largely those involving solvent extraction, because the nature of the metal complexes formed is usually best understood in such systems. NB. Extraction of lanthanides and actinides is not included as this subject is treated separately in Chapters 3.2 and 3.3. 

Several methods have been used to separate the lanthanides chemically solvent extraction, ion exchange chromatography, HPLC using Q-hydroxyisobutyric acid and, in limited cases, selective reduction of a particular metal cation.40-43 The use of di(2-ethylhexyl)orthophosphoric acid (HDEHP) for the separation of various rare-earth elements via solvent extraction has also been reported.44 16 This separation method is based on the strong tendency of Ln3+ ions to form complexes with various anions (i.e., Cl- or N03 ) and their wide range of affinities for com-plexation to dialkyl orthophosphoric acid. When the HDEHP is attached to a solid phase resin, the lanthanides can be selected with various concentrations of acid in order of size, with the smallest ion being the most highly retained. 

Baybarz, R. D. (1965). Dissociation contents of the transplutonium chelates with diethylenetriaminepentaacetic acid (DTPA) and the application of DTPA chelates to solvent extraction separations of transplutonium elements from the lanthanide elements, J. Inorg. Nucl. Chem. 27,1831. 

Clanex A solvent extraction process for converting solutions of the nitrates of actinides and lanthanides into their corresponding chlorides. The extractant is a solution of an aliphatic amine in diethylbenzene. 

We have considered typical examples of lanthanide and actinide solvent extraction by chelate formation, involving complexes with citric acid and with TTA, to prove that the labelling of a stable element by one of its radioactive isotopes can help to produce accurate data on the stability constants for complex formation. The method is applicable to elements with radioisotopes having a half-life allowing an ion concentration of 10 6m or less. Other methods of partition such as radiopolarography and radio-coulometry also result in accurate thermodynamical data when the same procedure of labelling is used (29). 

A guiding principle for the solvent extraction chemist is to produce an uncharged species that has its maximum coordination number satisfied by lipophilic substances (reactants). Eor trivalent lanthanides and actinides (Ln and An, respectively), the thermodynamic data suggest a model in which addition of one molecule of TBP displaces more than one hydrate molecule ... 

Albinsson, Y. Development of the AKUFVE-LISOL Technique. Solvent Extraction Studies of Lanthanide Acetylacetonates. Diss. Chalmers Univ. Techn., Gothenburg (1988). 

Americium may be separated from other elements, particularly from the lanthanides or other actinide elements, by techniques involving oxidation, ion exchange and solvent extraction. One oxidation method involves precipitation of the metal in its trivalent state as oxalate (controlled precipitation). Alternatively, it may be separated by precipitating out lanthanide elements as fluorosilicates leaving americium in the solution. Americium may also he oxidized from trivalent to pentavalent state by hypochlorite in potassium carbonate solution. The product potassium americium (V) carbonate precipitates out. Curium and rare earth metals remain in the solution. An alternative approach is to oxidize Am3+ to Am022+ in dilute acid using peroxydisulfate. Am02 is soluble in fluoride solution, while trivalent curium and lanthanides are insoluble. 

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. 

Byers, P. 1998. Novel extraction reagents for the solvent extraction of lanthanides and trivalent actinides. Ph.D. Thesis. University of Reading. 

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