Neodymium extractability

The method evolved by Moseley (1887 to 1915) of determining the atomic number enabled chemists to ascertain, as has already been seen, the maximum number of elements that can exist in serial order between any two selected ones. As the atomic numbers of lanthanum and lutecium are 57 and 71, it is clear that it is possible for 13 elements to exist of atomic numbers between these. Now europium was the twelfth to be discovered, but no element corresponding to 61 had been recorded. This should lie between neodymium (60) and samarium (62), and as early as 1902 Bohuslav Brauner had predicted its existence. In 1926 Hopkins, of Illinois, with his collaborators Harris and Yntema, announced the discovery of a new element in the neodymium extracted from monazite sand, the lines of the X-ray spectrum agreeing with those expected for element 61. He called it Illinium. 

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. 

Several other useful modifications of calciothermic reduction have been successfully developed for the preparation of this neodymium-bearing magnetic alloy. One of these is reduction-extraction which involves the reduction of neodymium sesquioxide (Nd203) with calcium in a molten calcium chloride-sodium chloride salt bath at 750 °C and the simultaneous extraction of the reduced metal into a molten neodymium-zinc or neodymium-iron alloy pool. The neodymium-zinc alloy product is treated in vacuum to remove zinc and produce neodymium metal, while the neodymium-iron alloy is itself the end product of... 

The leach liquor is first treated with a DEHPA solution to extract the heavy lanthanides, leaving the light elements in the raffinate. The loaded reagent is then stripped first with l.Smoldm nitric acid to remove the elements from neodymium to terbium, followed by 6moldm acid to separate yttrium and remaining heavy elements. Ytterbium and lutetium are only partially removed hence, a final strip with stronger acid, as mentioned earlier, or with 10% alkali is required before organic phase recycle. The main product from this flow sheet was yttrium, and the yttrium nitrate product was further extracted with a quaternary amine to produce a 99.999% product. 

Elemental composition Nd 85.73%, 0 14.27%. The oxide may he characterized hy x-ray diffraction and fluorescent properties. Neodymium may he analyzed in an acid extract of the oxide hy ICP-AES or ICP-MS techniques under appropriate dilution of the extract. 

Praesodymium may be recovered from its minerals monazite and bastana-site. The didymia extract of rare earth minerals is a mixture of praesodymia and neodymia, primarily oxides of praesodymium and neodymium. Several methods are known for isolation of rare earths. These are applicable to all rare earths including praesodymium. They include solvent extractions, ion-exchange, and fractional crystallization. While the first two methods form easy and rapid separation of rare earth metals, fractional crystaUization is more tedious. Extractions and separations of rare earths have been discussed in detail earlier (see Neodymium and Cerium). 

The solvent extraction of rare-earth nitrates into solutions of TBP has been used commercially for the production of high-purity oxides of yttrium, lanthanum, praseodymium and neodymium from various mineral concentrates,39 as well as for the recovery of mixed rare-earth oxides as a byproduct in the manufacture of phosphoric acid from apatite ores.272 273 In both instances, extraction is carried out from concentrated nitrate solutions, and the loaded organic phases are stripped with water. The rare-earth metals are precipitated from the strip liquors in the form of hydroxides or oxalates, both of which can be calcined to the oxides. Since the distribution coefficients (D) for adjacent rare earths are closely similar, mixer—settler assemblies with 50 or more stages operated under conditions of total reflux are necessary to yield products of adequate purity.39... 

Belair, S., Labet, A., Mariet, C., Dannus, P. 2005. Modeling of the extraction of nitric acid and neodymium nitrate from aqueous solutions over a wide range of activities by CMPO. Solvent Extr. Ion Exch. 23 (4) 481 199. 

Manchanda, V.K. Chang, C.A. Solvent extraction studies of lanthanum(III) and neodymium(III) with ionizable macrocyclic ligands and thenoyltrifluoroacetone, Anal. Chem. 58 (1988) 2269-2275. 

In the DMDBTDMA-alkane system (37, 140), the third phase is a gel when neodymium nitrate or thorium nitrate are extracted at high concentration, but... 

Selenophene /3-diketones containing a-, /3-, or y-pyridyl radicals can be used for extraction of neodymium the extraction percentage is approximately 90%. The most practical is w-picolinoyl-2-aceto-selenophene which gives a high percentage of metal extraction at a... 

A series of investigations (32-35, 101) on the extraction of these elements with carboxylic acids has been carried out by workers in the Soviet Union. Miller and associates (86) extracted lanthanides with 2,5-dimethyl-2-hydroxyhexanoic acid in chloroform. The heavy lanthanides after samarium were not extracted. In the extraction of neodymium the extracted species such as NdA3(HA)5 and Nd2A6(HA) were found together with small amounts of Nd2A6 and still smaller amounts of further aggregates (NdA3) - (86). 

The liquid-liquid extraction feed solutions were prepared by dilution of the neodymium nitrate stock solution with distilled water and nitric acid. These then were contacted with equal volumes of 1M HDEHP in separatory funnels, agitated for. 5 hr by a mechanical shaker, allowed to separate for. 5 hr, shaken another. 5 hr, then allowed to settle for 12 hr before the phases were separated carefully. A volumetric sample of the organic phase was back-extracted four times with an equal volume of 6M HN03. This solution was evaporated to dryness in order to remove the excess acid and then diluted to an appropriate concentration. The pH of this solution was adjusted to 3.0 to eliminate any hydrolysis effects... 

The nitrate ion activities in the aqueous phase were measured with a nitrate ion selective electrode taking into account the presence of high hydrogen ion concentration by calibration of the nitrate electrode with nitric acid. The nitrate ion concentration in the organic phase owing to the extraction of neodymium complexes by HDEHP was determined by back-extraction of the organic phase with 3M sulfuric acid, dilution, and analysis with a nitrate ion electrode calibrated for different nitrate and sulfate concentrations. The amount of the nitrate species extracted into the organic phase increases as the initial neodymium nitrate concentration increases. 

The neodymium ion concentration in the organic phase was measured by back-extraction with 6M nitric acid, removal of the neodymium by adsorption with the cation exchange resin, Dowex 50 x 8, and titration of the neodymium-free aqueous phase with NaOH using phenolphtalein... 

Fundamental studies have been reported using the cationic liquid ion exchanger di(2-ethylhexyl) phosphoric acid in the extraction of uranium from wet-process phosphoric acid (H34), yttrium from nitric acid solution (Hll), nickel and zinc from a waste phsophate solution (P9), samarium, neodymium, and cerium from their chloride solutions (12), aluminum, cobalt, chromium, copper, iron, nickel, molybdenum, selenium, thorium, titanium, yttrium, and zinc (Lll), and in the formation of iron and rare earth di(2-ethylhexyl) phosphoric acid polymers (H12). Other cationic liquid ion exchangers that have been used include naphthenic acid, an inexpensive carboxylic acid to separate copper from nickel (F4), di-alkyl phosphate to recover vanadium from carnotite type uranium ores (M42), and tributyl phosphate to separate rare earths (B24). 

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