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- Author or Editor: K.A. Venkatesan x
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Abstract
The amphoteric acid-base behavior of hydrous zirconium oxide (HZO) was investigated by titrating HZO with 0.05M HNO3 and NaOH at constant ionic strength. The sorption of strontium from 0.05M NaNO3 solution was measured as a function of pH. Abrupt increase in sorption was observed at the equilibrium pH of 9. The experimental titration and strontium sorption data on HZO were evaluated using the constant capacitance model (CCM) and diffuse double layer model (DLM). Various model parameters of Surface Complexation Models (SCM) were estimated, numerically, by non-linear regression. Modeling the sorption and speciation of Sr2+ on HZO indicated that the hydrolysis of Sr2+ to lower charged SrOH+ is the pre-requisite for the abrupt sorption behavior at pH 9.
Abstract
High-level liquid waste from fast reactor fuel reprocessing stream contains significant quantities of lanthanides and trivalent minor actinides. The lanthanides and minor actinides (MA) have been separated from the fast reactor high-level liquid waste (FR-HLLW) using TRUEX solvent, which is a mixture of 0.2 M octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO)-1.2 M tri-n-butylphosphate (TBP) in n-dodecane. A new stripping composition, 0.1 M HNO3 and 0.1 M citric acid (CA), has been employed for back extraction of them from the TRUEX solvent. In order to separate lanthanides from actinides present in the strip solution, the extraction behavior of 241Am(III) and (152+154)Eu(III) from CA–HNO3 medium by a solution of bis-2-ethylhexylphosphoric acid (HDEHP) in n-dodecane has been studied. Separation factors (SF = D Eu/D Am) has been reported as a function of various parameters such as pH, concentrations of HDEHP, diethylenetriamine-N,N,N′,N′′,N′′′-pentaaceticacid (DTPA), 1-octanol and TBP in this paper.
Summary
A systematic study on the extraction of U(VI) from nitric acid medium by tri-n-butylphosphate (TBP) dissolved in a non-traditional diluent namely 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6) ionic liquid (IL) is reported. The results are compared with those obtained using TBP/n-dodecane (DD). The distribution ratio for the extraction of U(VI) from nitric acid by 1.1M TBP/bmimPF6 increases with increasing nitric acid concentration. The U(VI) distribution ratios are comparable in the nitric acid concentration range of 0.01M to 4M, to the ratios measured using 1.1M TBP/DD. In contrast to the extraction behavior of TBP/DD, the D values continued to increase with the increase in the concentration of nitric acid above 4.0M. The stoichiometry of uranyl solvate extracted by 1.1M TBP/IL is similar to that of TBP/DD system, wherein two molecules of TBP are associated with one molecule of uranyl nitrate in the organic phase. Ionic liquid alone also extracts uranium from nitric acid, albeit to a small extent. The exothermic enthalpy accompanying the extraction of U(VI) in TBP/bmimPF6 decreases with increasing nitric acid and with TBP concentrations.
Summary
Commercially available polystyrene-divinylbenzene (PS-DVB) resins functionalized with isothiouronium (Tulsion CH-95), phosphinic acid (Tulsion CH-96) and methylene thiol (Tulsion CH-97) moieties have been used for separating palladium from nitric acid medium. Extraction of palladium has been studied as a function of time, concentration of nitric acid and palladium. The distribution coefficients (K d, ml/g) of palladium on sulfur based resins (Tulsion CH-95 and Tulsion CH-97) are higher (5000-104ml/g in 0.1M nitric acid) than on Tulsion CH-96 resin and decrease with increasing concentration of nitric acid. The initial rate of extraction of palladium by Tulsion CH-95 and Tulsion CH-97 resins was very rapid and the time required for the establishment of equilibrium was a function of palladium concentration in the aqueous phase. The rate data could be fitted by a second order rate equation and the magnitude of rate constant for the extraction of palladium by these resins (~102M-1. min-1) decreased in the order of: Tulsion CH-95 > Tulsion CH-97 > Tulsion CH-96. The extraction isotherms of Tulsion CH-95 were fitted by Langmuir adsorption model and the coefficients were obtained by regression. The extraction capacity of palladium on Tulsion CH-95 was found to be ~20 mg/g at 3M nitric acid. Column experiments have been conducted and the data were fitted using Thomas model. A column utilization of 75% was achieved for the extraction of palladium by Tulsion CH-95 resin.
