Lanthanide HDEHP extraction

Preconcentration by an acidic organophosphorus extractant is also effective, though the lanthanides are extracted from dilute acid solutions (10 -10 M) and stripped into acidic (>1M) solutions when HDEHP is employed as the extractant. A representative application of liquid-liquid extraction to rare-earth preconcentration is the 100 to 200-fold concentration of the rare earths in seawater prior to ICP/MS determination using a mixture of HDEHP and mono-(2-ethylhexyl)phosphoric acids (Shabani et al. 1990, Shabani and Masuda 1991). When the same extractant system was adsorbed on a Cig cartridge and used in an extraction chromatographic mode, the rare earths were concentrated 200-1000-fold (Shabani et al. 1992). 

Sample solutions measuring 50 pi were mixed with 350 pi 5 M HNO3 and 2.4 ml 0.1 M A1 (NOaja. The aluminum nitrate was used to complex fluoride ions. and disturbing nuclides (mainly lanthanides) were extracted into 1.0 M HDEHP (bis-2-ethylhexyl orthophosphoric acid) in Solvent 70 (an aliphatic kerosene) 2.0 ml of the aqueous phase was taken out, and... 

Separation factors for trivalent lanthanide/actinide extraction by HDEHP/ toluene (Stary 1966) and HDEHP/kerosine (Sato 1989). 

A promising application of HDEHP extraction appears to lie in the partitioning of actinides from lanthanides. The TALSPEAK process (Trivalent Actinide Lanthanide Separation by Phosphorus Reagent Extraction from Aqueous Komplexes) involves extraction of Ln s with HDEHP from an aqueous solution of a complex (such as DTPA) which has a high affinity for and represses extraction of the middle and heavier lanthanons and actinide elements most of all . The separation factor between the An s, Am and Cm ", and the Ln s exceeds 100. 

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. 

A mixture of well-known extractants, di-(2-ethylhexyl)phosphoric acid (HDEHP) and CMPO, in n-paraffin was used for the study of combined extraction of different actinides (americium, plutonium, and uranium) and lanthanides (cerium and europium) and their separation from fission products (cesium, strontium, ruthenium, and zirconium).54 Combined extraction of MAs and lanthanides was studied together with group separation of MAs from lanthanides by selective stripping with a solution of diethylenetriaminepentaacetic acid (DTPA), formic acid, and hydrazine hydrate. This solution strips only MAs, leaving lanthanides in the organic phase. Subsequently, the lanthanides are stripped using a mixture of DTPA and sodium carbonate. 

Di(2-ethylhexyl) phosphoric acid (HDEHP) is an extractant molecule used for An(III)/Ln(III) separation. Used in TALSPEAK-type processes in a mixture with TBP, or in the DIAMEX-SANEX process in a mixture with a malonamide (154-157), it has also been proposed, in a mixture with TBP, to remove strontium from PUREX acid waste solution in the Hanford B plant (158). Therefore, numerous studies have focussed on the radiolytic degradation of HDEHP and its effects on the extraction of Sr(II), lanthanides(III), and actinides(III) (10, 158-163). 

An initial experiment involving the treatment of small irradiated Pu/Al targets for the production of americium 243 and curium 244 was carried out in France in 1968 (2). The chemical process was based essentially on the use of a system comparable to the Talspeak system. After plutonium extraction by a 0.08 M trilaurylammonium nitrate solution in dodecane containing 3 vol % 2-octanol, the actinides (americium, curium) were coextracted with a fraction of the lanthanides by a 0.25 M HDEHP -dodecane solvent from an aqueous solution previously neutralized by A1(N0 ) x(0H)x and adjusted to 0.04 M DTPA. The actinides were selectively stripped by placing the organic phase in contact with an aqueous solution of the composition 3 M LiN0 -0.05 M DTPA. While this experiment achieved the recovery of 150 mg of americium 243 and 15 mg of curium 244 with good yields, the process presented a drawback due to the slow extraction of Al(III) which saturates the HDEHP. This process was therefore abandoned. 

Typical cation exchange extractants are di-2-ethylhexylorthophosphoric acid (HDEHP), di-n-octyl orthophosphoric acid (HDOP) and hexylphenyl phosphonic acid (HEHP). Some data on the separation factors for adjacent pairs of lanthanides are given in Table 1.22. 

The separation of transplutonium elements from the lanthanides constitutes the delicate phase of chemical treatment, owing to their comparable affinities for the usual extractants HDEHP, TBP and TLAHNO3. Among all the systems described in the literature and covered by a recently published critical compilation (JO), we selected those which appeared to be much suitable for adaptation to extraction chromatography the Talspeak process (7) and the... 

The acid dependency observed in practice hal been only approximately inverse third power. Impurities in Cleanex feed solutions often cause a departure from ideality (e.g., by common-ion effect or by consumption of some of the HDEHP), and we have not been able to control the extraction of the actinide elements solely by monitoring the aqueous-phase acidity. Fortunately, when processing transplutonium elements, the high specific activity of 21+I+Cm facilitates the detection of that isotope in both phases, thus permitting a rapid determination of the degree of extraction. The extraction coefficients of the trivalent actinides and lanthanides are all quite similar, so the 21+1+Cm serves as an excellent marker for all the extracted ions. 

Experimental studies were therefore directed to investigate the removal of actinides from both diluted (5000 l/t) and concentrated (about 500 l/t) HAW solutions. Three alternative processes have been selected for this purpose. They all rely upon actinide separation at low acidity conditions requiring a preliminary denitration step. Two of them (TBP and HDEHP processes) are based on solvent extraction techniques using as extractants a neutral (TBP) and an acidic (HDEHP) organophosphorus compound respectively. The third process (OXAL) applies as the first step the precipitation of actinides and lanthanides FP as oxalates. 

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