Ankita Rao

Study of effects of different parameters on supercritical fluid extraction of uranium from acidic solutions employing TBP as co-solvent

Abstract In the supercritical fluid extraction of uranium from acidic medium employing TBP as co-solvent, effects of various parameters on extraction efficiency were studied. Variation in pressure (80–300 atm), temperature (308–353 K), CO2 flow rate (0.5–3 mL/min), co-solvent percentage (1–10%), molarity of nitric acid (0.5–10 M) were found to influence uranium extraction efficiency. The uranium extraction efficiency depends on distribution ratio and kinetics of transport of U-TBP complex into supercritical CO2. In the 150–300 atm pressure range, variation in extraction efficiency was similar to that of uranium distribution ratio under equilibrium conditions. Whereas below 150 atm, it closely followed supercritical CO2 density variation which could be attributed to non-equilibrium behavior that eventually attained equilibrium. In the non-equilibrium region, increased supercritical CO2 density with pressure favored enhancement in solubility as well as extraction kinetics of the U-TBP complex. Increase in temperature generally resulted in enhanced volatility of U-TBP complex and a decrease in supercritical CO2 density which in turn affected the extraction efficiency. Up to 333 K temperature, extraction efficiency gradually increased due to enhancement in volatility of U-TBP complex which more than compensates for decrease in the supercritical CO2 density. Beyond this temperature, the steep fall in the extraction efficiency is attributed to combined effect of saturation in volatility of the U-TBP complex and significant decrease in the density of supercritical CO2 approaching the critical value at which supercritical CO2 tends to form large clusters thereby resulting in steep decrease in its solvating power. Extraction efficiency was found to increase with nitric acid molarity up to 7 M and afterwards showed small decrease possibly due to competitive co-extraction of HNO3. Up to CO2 flow rate of 1 mL/min increase in extraction efficiency was observed which attained saturation afterwards. Linear increase in extraction efficiency was observed with the amount of TBP. Extraction efficiency was found to increase linearly with logarithm of extraction time. Under optimised conditions (150 atm, 333 K, 1 mL/min CO2 flowrate, 10% co-solvent, 7 M nitric acid and 30 min dynamic extraction time) extraction efficiency was found to be (98±2) was observed. 30 min dynamic extraction mode was found equivalent to 40 min static mode. Online complexation mode was more efficient than in situ mode.

Supercritical Carbon Dioxide Extraction of Uranium from Acidic Medium Employing Calixarenes

Various calixarenes were evaluated for the supercritical fluid extraction of uranium from nitric acid medium. The extraction efficiency was found to be affected by various parameters, namely pressure, temperature, CO2 flowrate, extraction time, and molarity of nitric acid. The addition of HPFOA (pentadecafluoro-n-octanoic acid) for the production of CO2-phillic fluorinated counter ion enhanced the extraction efficiency. Under optimized conditions (pressure of 200 atm, temperature of 323 K, 30 minutes of static time followed by 30 minutes of dynamic time, CO2 flowrate of 2 mL min−1, nitric acid molarity of 0.1 M) for uranium: calixarene: HPFOA mole ratio of 1:5:10, highest extraction efficiency could be obtained with p-tert.-butyl calix[6]arene (79.9%). Solvent extraction study with hexane as the organic phase indicated the formation of [UO2 (calixarene)]2+. In order to assess the suitability of the developed method to extract uranium in the presence of a host of other ions, extraction efficiency for other metal ions was estimated.

Supercritical fluid extraction of thorium from tissue paper matrix employing β-diketones

Abstract Various β-diketones viz. acetylacetone (AA), trifluoroacetylacetone (TFA), hexafluoroacetylacetone (HFA), thenoyltrifluoroacetylacetone (TTA) and heptafluorobutanoylpivaroylmethane (FOD) were evaluated as chelating agents for the supercritical fluid extraction of thorium from tissue paper matrix. In-situ chelation mode was found to be more effective than online chelation mode. A combination of tributyl phosphate (TBP) and β-diketones further enhanced the extraction efficiency. The extraction efficiency trend observed in all the cases was: TTA>FOD>HFA>TFA>AA. A correlation was observed between extraction efficiency and degree of fluorination in the side arms of β-diketones. This could be attributed to the fact that in supercritical CO2, higher fluorination results in higher percentage of enol content, greater dissociation into enolate ion and higher solubility and stability of β-diketones as well as of Th-β-diketone chelates. Highest extraction efficiency with TTA was probably due to the presence of aromatic thenoyl group. The spectra of the extracted Th-chelates displayed peaks in the visible region, which shifted towards UV region with increasing fluorination. In the Th-TTA chelate spectrum, red shift was observed.

Complexation with calixarenes and efficient supercritical CO2 extraction of Pb(II) from acidic medium

The present study describes the extraction of lead(II) from acidic medium with supercritical carbon dioxide using various calixarenes. It involves the investigation of the effect of temperature, acid molarity, and the metal to complexing agent molar ratio on supercritical fluid extraction efficiency. Efficient extraction of Pb(II) was observed for p-t-butylcalix(4)arene with (92 ± 3)% extraction at 323 K, 20.27 MPa, 30 minute static time followed by 30 minute dynamic time and a metal to complexing agent molar ratio of 1:5. The complexing ability of Pb(II) with calixarene was established by absorption and energy dispersive spectroscopy. The scanning electron micrograph of calixarene and the lead–calixarene complex was studied. The structure of the Pb(II)–calixarene complex has been proposed based on solvent extraction in hexane and IR spectroscopic analysis of the extract. Thermodynamic aspects of extraction were also studied and the extraction reaction was found to be entropy driven. Interference from other metal ions, on Pb(II) extraction behaviour, has been investigated. The developed method has been utilized for extraction of Pb(II) from real samples viz. paints, batteries, tobacco and wastewater.

Supercritical carbon dioxide extraction of uranium from acidic medium employing crown ethers

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) %.

Studies on separation and purification of fission 99Mo from neutron activated uranium aluminum alloy

A new method has been developed for separation and purification of fission (99)Mo from neutron activated uranium-aluminum alloy. Alkali dissolution of the irradiated target (100mg) results in aluminum along with (99)Mo and a few fission products passing into solution, while most of the fission products, activation products and uranium remain undissolved. Subsequent purification steps involve precipitation of aluminum as Al(OH)3, iodine as AgI/AgIO3 and molybdenum as Mo-α-benzoin oxime. Ruthenium is separated by volatilization as RuO4 and final purification of (99)Mo was carried out using anion exchange method. The radiochemical yield of fission (99)Mo was found to be >80% and the purity of the product was in conformity with the international pharmacopoeia standards.