Separation of Rare-Earth Elements from Nitrate Solutions by Solvent Extraction Using Mixtures of Methyltri-n-octylammonium Nitrate and Tri-n-butyl Phosphate

The article presents data on the solvent extraction separation of rare-earth elements (REEs), such as La(III), Ce(III), Pr(III), and Nd(III), using synergic mixtures of methyltrioctylammonium nitrate (TOMANO3) with tri-n-butyl phosphate (TBP) from weakly acidic nitrate solutions. Specifically, experimental results on separation of REEs, for the pair Ce(III)/Pr(III) for quaternary mixtures of REEs (La(III), Ce(III), Pr(III), Nd(III)) and for the pair La(III)/Pr(III) for solutions containing La(III), Pr(III), and Nd(III), are presented. It was shown that effective separation for the pair Ce(III)/Pr(III) from a solution containing 219 g Ce(III)/L, 106 g La(III)/L, 20 g Pr(III)/L, 55 g Nd(III)/L, and 0.1 mol/L HNO3, was achieved using 56 steps of a multistage, counter-current solvent extraction cascade with scrubbing, at an organic-to-aqueous phase volume ratio (O/A) equal to 2/1 on the extraction section and O/A equal to 4/1 on the scrubbing section, using 3.3 mol/L solutions of the mixture TOMANO3-TBP with molar ratio 0.15:0.85 in dodecane. Separation for the pair La(III)/Pr(III) could be achieved using a solvent extraction cascade with scrubbing in 32 steps at O/A equal to 2/1 on the extraction section and O/A equal to 2.8/1 on the scrubbing section of the solvent extraction cascade from a solution containing 258 g La(III)/L, 58 g Pr(III)/L, 141 g Nd(III)/L, and 0.1 mol/L HNO3 with 3.0 mol/L solution of the mixture TOMANO3-TBP with molar ratio 0.2:0.8 in dodecane.

Research on obtaining gadolinium oxide from waste technologies for processing of uranium-gadolinium containing materials

One of the activities of the Uranium production of JSC “UMP” is the processing of hard-to-open uranium-gadolinium-containing scraps. When processing materials of this type, after their dissolution, the gadolinium fluoride precipitation operation is carried out with the subsequent extraction purification of the obtained uranyl nitrate solutions. At the deposition stage, almost all the gadolinium contained in the scraps is transferred to the GdF3 precipitate and sent to the tailings dump as part of the solid waste. In order to determine the possibility of obtaining gadolinium oxide from waste processing of uran-gadolinium containing materials, exploratory studies were initiated. In the course of the work, various methods of obtaining gadolinium oxide were tested. A number of experiments were carried out to refine the modes of obtaining gadolinium oxide by the method of two-stage precipitation of oxalate. A technological scheme was developed, according to which a finished product was obtained, suitable for further use in the technology of obtaining uranium-gadolinium tablets of UMP JSC. The scheme consists of the following main operations: dissolution of gadolinium fluoride in a solution of aluminum nitrate, precipitation of gadolinium oxalate, washing of gadolinium oxalate in the first stage of precipitation with a solution of nitric acid, conversion of oxalate to gadolinium hydroxide, dissolution of hydroxide in a solution of nitric acid, re-precipitation of gadolinium oxalate, calcination to gadolinium oxide.

DISTRIBUTION OF THORIUM (IV) IONS IN AQUEOUS EXFOLIATING SYSTEM CONTAINING ANTIPYRINE AND SULFOSALICYLIC ACID

The possibilities of an aqueous delaminating system containing antipyrine (AP) and sulfosalicylic acid (SSA) for extracting macro - and microamounts of thorium (IV) were studied. The proposed extraction system eliminates the use of toxic organic solvents. The dependences of the distribution of metal from nitrate solutions between phases on the concentration of reagents, acidity of the medium, the amount of inorganic salting-out agent (NaNO3, NH4NO3, Na2SO4) and the volume of the aqueous phase are determined, and optimal conditions for extraction are found. It is shown that in the organic phase with a volume of 1.6 ml at room temperature, macro-and microamounts of thorium (IV) are extracted by 88 and 90%, respectively. The maximum extraction of the cation is achieved at the ratio of AP: SSA = 2.0 : 1.0 and their concentration, mol/l: 0.6: 0.3, while the acidity of the medium created by nitric acid should be equal to 0.015 mol/l (pHequ. = 1.8-1.9). The extraction of thorium (IV) becomes quantitative if inorganic salts (sodium sulfate, sodium nitrate) are introduced into the AP – SSA – 0,015 mol/l HNO3 – H2O system, which, by reducing the activity of water, increase the concentration of reagents in the aqueous phase. The concentration of salting-out agents should correspond to 1.0 and 2.5 mol/l. A mechanism for the distribution of a mixed thorium (IV) complex containing AP, SSA, nitrate ions, solvated with a salt of antipyrinium sulfosalicylate is proposed. The extract is mixed in any relationship with distilled water, providing the use of various instrumental methods of analysis. A method for extraction-photometric determination of thorium (IV) with a toron indicator has been developed. The limit for the fulfillment of the Bouguer-Lambert-Beer law is established. The apparent coefficient of light absorption is calculated (ε = 1.7∙104).

Calixresorcin[4]arene-Mediated Transport of Pb(II) Ions Through Polymer Inclusion Membrane

A facilitated transport of Pb(II) through polymer inclusion membrane (PIM) containing 1,8,15,22-tetra(1-heptyl)-calixresorcin[4]arene and its tetra- and octasubstituted derivatives containing phosphoryl, thiophosphoryl or ester groups as an ion carrier was investigated. The efficiency of Pb(II) removal from aqueous nitrate solutions was considered as a function of the composition of membrane (effect of polymer, plasticizer, and carrier), feed (effect of initial metal concentration and presence of other metal ions) and stripping phases, and temperature of the process conducting. Two kinetic models were applied for the transport description. The highest Pb(II) ions removal efficiency was obtained for the membrane with tetrathiophosphorylated heptyl-calixresorcin[4]arene as an ion carrier. The activation energy value, found from Eyring plot to be equal 38.7 ± 1.3 kJ/mol, suggests that the transport process is controllable both by diffusion and chemical reaction. The competitive transport of Pb(II) over Zn(II), Cd(II), and Cr(III) ions across PIMs under the optimal conditions was also performed. It was found that the Cr(III) ions’ presence in the feed phase disturb effective re-extraction of Pb(II) ions from membrane to stripping phase. Better stability of PIM-type than SLM-type membrane was found.