Abstract
Abstract Supercritical carbon dioxide (SC CO2) extraction of uranium from nitric acid medium employing various crown ethers was studied. CO2-phillic C–F bonds in pentadecafluoro-n-octanic acid (HPFOA) counter ion enhanced the extraction efficiency. Pressure (100−300 atm) and temperature (323−353 K) were found to influence extraction efficiency by affecting SC CO2 density as well as due to large size cluster formation of supercritical fluid near critical point thereby resulting in reduced interaction with solute. Pressure of 200 atm and temperature of 323 K were found to be optimum. The trend in efficiency for benzo substituted crown ethers was due to the combined effect of cavity size and number of ether oxygen atoms. The extraction efficiency among 18-crown-6 series is influenced by the extent of basicity of ether oxygen, which in turn is dictated by the substituent group. Efficiency also decreased beyond 2 M nitric acid due to co-extraction of crown-nitric acid complex. Uranium: crown: HPFOA mole ratio influenced extraction efficiency, having optimum value at 1:10:100. Under optimized conditions with ditertiarybutyldicyclohexano-18-crown-6 the efficiency was found to be (86±5) %.
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