No abstract

Analysis of exploration materials and market conditions showed that by-product recovery of rhenium, one of the rarest strategic elements of the periodic system, was not always effective in processing the whole volume of pregnant uranium-bearing solutions. The main goal of the research was to develop an effective method for recovery rhenium from pregnant solutions in in-situ uranium leaching. The objectives of the research were as follows: evaluation of the possibility of selective-and-advanced recovery of rhenium from ores by in-situ leaching method and comparison of the technological advantages of the new proposed method with the known ones. The study involved the analysis of historical geological, mineralogical and geochemical information on the Dobrovolnoye deposit and analysis of technological aspects of by-product recovery of rhenium in the world practice. A selective-and-advanced scheme of rhenium recovery from pregnant uranium-bearing sulfate (sulfuric acid) solutions of the Dobrovolnoye deposit ISL (Russia) using mobile installations was proposed. The process has the following features: zoning of production blocks when constructing injection and extraction (pumping) wells; piping of selective extraction wells into a separate collecting pipe; implementation of advanced rhenium sorption. The process implementation makes it possible to obtain rhenium from economically viable areas of the uranium deposit. The mobile installation includes the following main units: a filter for purification (aftertreatment) to remove suspension, a chain of sorption apparatuses (sorption filters or columns), connecting fittings, control and measuring instruments. The sorption apparatuses are filled with rhenium-selective ionite (ion exchanger). As a selective sorbent for the primary concentration of rhenium from sulfate solutions (pH 2), weakly basic nitrogen-bearing ionites containing amine functional groups of various types can be used. If further concentration of rhenium is required, in order to unify the equipment used, materials with a mobile extractant phase (so-called TVEXs (solid extractants or Levextrel resins in English literature) and so-called “impregnated” or “impregnates”), such as TVEX-DIDA containing diisododecyl amine, or TAA-impregnate containing trialkylamine, can be used. Rhenium desorption from these materials is carried out by an ammonia solution, which allows producing rough ammonium perrhenate from the eluate. Economic aspects of the rhenium selective-andadvanced technology were evaluated. Implementation of the recovery selective-and-advanced technology allows obtaining rhenium from economically-viable areas of the uranium deposit.

The possibility of using the short-lived radioisotope 188Re (16.9 h) in the radioactive-tracer technique for estimation of the losses occurred during sample preparation and for analysis of the solutions with a low rhenium content is shown. The radioisotope was obtained in an 188Re generator, which is a glass column filled with aluminum oxide with a pre-adsorbed parent isotope 188W (69.4 days) that forms 188Re during β-decay. The latter in the form of a perrhenate ion was selectively washed into an aqueous solution, which was used to obtain a labeled solution. The values of rhenium losses and their distribution over the stages of sample preparation of carbon-containing raw materials (e.g., high-viscosity oil) including sintering, leaching, filtration and evaporation are estimated. It is shown that the greatest amount of rhenium is lost at the stage of sintering. However, the use of MgO + KMnO4 mixture minimize the losses occurred at this stage and, hence, the total losses of rhenium. A rapid procedure of rhenium determination using the method of radiometric correction with substoichiometric separation is described. The method is based on the quantitative extraction of a stable complex of tetraphenylphosphonium cation (TPhPh) with the perrhenate ion by dichloroethane. The extraction constant of (C6H5)4PReO4 complex is (3.03 ± 0.75) × 106. The extraction of the perrhenate ion not complexing with TPhPh does not exceed 1 – 2 %. The developed method provides rhenium determination in the sample at a level of 1 – 100 μg. A 10-fold excess of Zn2+ and Ni2+ present in a chloride-containing medium affects the determination of rhenium. The anions , , and have the most pronounced interfering effect whereas , , and Cl– do not interfere with the determination.