Sujoy Biswas

Development of an extractive spectrophotometric method for estimation of uranium in ore leach solutions using 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A) and tri-n-octyl phosphine oxide (TOPO) mixture as extractant and 2-(5-bromo-2-pyridylozo)-5-diethyl aminophenol (Br-PADAP) as chromophore

An extractive spectrophotometric analytical method has been developed for the determination of uranium in ore leach solution. This technique is based on the selective extraction of uranium from multielement system using a synergistic mixture of 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A) and tri-n-octyl phosphine oxide (TOPO) in cyclohexane and color development from the organic phase aliquot using 2-(5-Bromo-2-pyridylazo)-5-diethyl aminophenol (Br-PADAP) as chromogenic reagent. The absorption maximum (λ(max)) for UO(2)(2+)-Br-PADAP complex in organic phase samples, in 64% (v/v) ethanol containing buffer solution (pH 7.8) and 1,2-cyclohexylenedinitrilotetraacetic acid (CyDTA) complexing agent, has been found to be at 576 nm (molar extinction coefficient, ɛ: 36,750 ± 240 L mol(-1)cm(-1)). Effects of various parameters like stability of complex, ethanol volume, ore matrix, interfering ions etc. on the determination of uranium have also been evaluated. Absorbance measurements as a function of time showed that colored complex is stable up to > 24h. Presence of increased amount of ethanol in colored solution suppresses the absorption of a standard UO(2)(2+)-Br-PADAP solution. Analyses of synthetic standard as well as ore leach a solution show that for 10 determination relative standard deviation (RSD) is < 2%. The accuracy of the developed method has been checked by determining uranium using standard addition method and was found to be accurate with a 98-105% recovery rate. The developed method has been applied for the analysis of a number of uranium samples generated from uranium ore leach solutions and results were compared with standard methods like inductively coupled plasma emission spectrometry (ICPAES). The determined values of uranium concentrations by these methods are within ± 2%. This method can be used to determine 2.5-250 μg mL(-1) uranium in ore leach solutions with high accuracy and precision.

Quaternary ammonium based task specific ionic liquid for the efficient and selective extraction of neptunium

Abstract: Liquid–liquid extraction of neptunium from aqueous acidic solution using quaternary ammonium based task specific ionic liquid (TSIL) was investigated. The extraction of Np was predominated by the ‘cation exchange’ mechanism via [NpO2·Hpth]+ species for NpO22+, while NpO2+ was extracted in ionic liquid as [NpO2·H·Hpth]+. The extraction process was thermodynamically spontaneous while kinetically slower. Na2CO3 as strippant showed quantitative back extraction of neptunium ions from TSIL. TSIL showed excellent radiolytic stability upto 500 kGy gamma exposure. Finally, the TSIL was employed for the processing of simulated high level waste solutions revealing high selectivity of TSIL towards neptunium.

Uranium Permeation from Nitrate Medium Across Supported Liquid Membrane Containing Acidic Organophosphorous Extractants and their Mixtures with Neutral Oxodonors

Permeation of U(VI) from nitric acid solution has been studied across supported liquid membrane (SLM) using bis[2,4,4 trimethyl pentyl] phosphinic acid (Cyanex 272) either alone or in combination with neutral donors like Cyanex 923 (a mixture of four trialkyl phosphine oxides viz. R3PO, R2R′PO, RR′2PO, and R′3PO where R: n-octyl and R′: n-hexyl chain), TBP (tri-n-butyl phosphate), and TEHP (tris-2-ethylhexyl phosphate) dissolved in n-paraffin as carriers. Effect of various other parameters such as nature and concentration of receiver phase, feed acidity, uranium concentration, pore size, and membrane thickness on U(VI) transport across SLM were investigated. Transport behavior of U(VI) was also compared with other derivatives of phosphoric acids like 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A), dinonyl phenyl phosphoric acid (DNPPA) under identical conditions and it followed the order: Cyanex 272 > PC88A > DNPPA. 2 M H2SO4 was suitable for effective U(VI) transport across SLM. Presence of neutral donors in carrier showed significant enhancement in U(VI) permeation in the order: Cyanex 923 > TBP > TEHP. U(VI) transport decreased with increased membrane thickness as well as decrease in pore size. The optimized conditions were tested for recovery of U(VI) from uranyl nitrate raffinate (UNR) waste generated during purification of uranium.

Uranium Permeation Studies from Nitric Acid Medium across Supported Liquid Membrane Impregnated with PC88A and its Mixtures with Neutral Oxodonors in n-paraffin as Carriers

The permeation of U(VI) from nitric acid medium using supported liquid membrane (SLM) technique has been studied employing varying compositions of feed (uranium concentration and acidity), carrier, and receiving phase. Microporous polytetrafluoroethylene (PTFE) membranes were used as a solid support and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC88A) either alone or as a mixture of neutral donors like tri-n-butyl phosphate (TBP), tris(2-ethylhexyl) phosphate (TEHP), and tri-n-octyl phosphine oxide (TOPO) dissolved in n-parrafin as the carrier. Oxalic acid/Na2CO3 solutions were used as the receiving phase. The permeability coefficient (P) of U(VI) decreased with increased nitric acid concentration up to 3 M HNO3 and thereafter increased up to 5 M HNO3. Uranium permeation was also investigated from its binary mixtures with other metal ions such as Zr(IV), Th(IV), and Y(III) at 2 M HNO3 employing 0.1 M PC88A/n-paraffin as the carrier, and 0.5 M oxalic acid as the receiver phase. The presence of neutral donors in the carrier solution enhanced the permeation of U(VI) across the SLM in the following order: TEHP ∼ TBP > TOPO using 0.1 M oxalic acid as receiver phase. There was significant enhancement in uranium transport for feed acidity ≤2 M HNO3 employing 1 M Na2CO3 as the receiver phase. These studies suggested that 0.1 M PC88A and 0.5 M oxalic acid as carrier and receiver phases appear suitable for selective and faster transport of uranium from the uranyl nitrate raffinate (UNR) waste solutions.

Quaternary ammonium-based task-specific ionic liquid: An efficient and ‘green’ separation for ‘f block’ elements

ABSTRACT Functionalized ionic liquid based on quaternary ammonium salt was investigated for the specific task of the efficient extraction of f block elements in different oxidation states. It deals with the investigation of extraction efficiency, mechanism, speciation and associated kinetics and thermodynamics. The extracted species of Pu4+, PuO22+, Am3+, Eu3+ were found to be Pu(Hptha)(H2O)63+, PuO2(Hptha)(H2O)2+, Am(Hptha)(H2O)72+, Eu(Hptha)(H2O)72+, respectively where (Hptha)− is the anionic part of the ionic liquid. Effect of radiation exposure on the performance of the ionic liquid was also investigated. The suitable back extraction procedure from the ionic liquid phase was developed using aqueous soluble complexing agents.

Comparative Evaluation of Tri-n-butyl Phosphate (TBP) and Tris(2-ethylhexyl) Phosphate (TEHP) for the Recovery of Uranium from Monazite Leach Solution

Separation of U(VI) from Th(IV) and rare earth elements (REEs) present in monazite leach solution (nitric acid medium) has been studied using tris(2-ethylhexyl) phosphate (TEHP) and tri-n-butyl phosphate (TBP) dissolved in n-paraffin as solvents under varying experimental conditions such as nitric acid, extractant and metal ion concentrations etc. There is an increase in distribution ratio of U(VI) (D U ) with increase in aqueous phase acidity up to 5 M HNO3 beyond which a decrease is observed. Typically for 1 × 10−3 M U(VI), the DU values increase from 8 (0.5 M HNO3) to 80 (5 M HNO3) for 1.1 M TEHP, and from 2 (0.5 M HNO3) to 43 (5 M HNO3) for 1.1 M TBP in n-paraffin. The separation factors of U(VI) (β: DU/DM) over metal ions (M) such as Th(IV) and Y(III) (chosen as a representative of heavy REEs) are better for TEHP than TBP at all nitric acid concentrations. Batch solvent extraction data have been used to construct the McCabe-Thiele diagrams for the recovery of U(VI) employing TEHP as the extractant. A process flow sheet has been proposed with 0.2 M TEHP in n-paraffin as solvent for the recovery of U(VI) from simulated monazite leach solution in HNO3 medium.

Development of a 99Mo/99mTc generator using alumina microspheres for industrial radiotracer applications

A chromatographic (99)Mo/(99m)Tc generator for industrial applications has been developed using alumina microspheres synthesized through sol-gel process to obtain (99m)Tc in both aqueous and non-aqueous media. The sorbent was mesoporous, mechanically strong and possessed high surface area. (99m)Tc could be eluted from generator system using either acetone or 0.9% NaCl solution with appreciably high yields and high radiochemical as well as radionuclidic purity. The facile, versatile generator provides an efficient way to access (99m)Tc at industrial sites for radiotracer applications.

Separation and Recovery of Uranium from Wastewater Using Sorbent Functionalized with Hydroxamic Acid

A newly developed hydroxamic acids functionalized acrylic based solid phase sorbent, named as poly-acryl hydroxamic acid (PHOA) is used as an extractant for the recovery of uranium from nuclear waste solution. Various parameters such as sorbent solubility in different medium, effect of various cations on U(VI) sorption, desorption performance of different eluents with respect to U(VI) sorption has been investigated in detail. U(VI) sorption behaviors of the sorbent were studied in different concentration of competitive ions such as Mg2+, Fe3+, and NO3− and it was found that the sorbent was capable of removing the U(VI) efficiently in the presence of high concentration of these ions.

Effects of alkyl substituents of organophosphorous extractants on uranium permeation for recovery from uranyl nitrate raffinate

ABSTRACT Carrier mediated transport of uranium from nitric acid medium has been investigated using supported liquid membrane (SLM). Microporous polytetrafluoroethylene (PTFE) membrane (pore size: 0.45 μm, diameter: 47 mm, unless stated otherwise) was used as a solid support and various neutral donor organophosphorous extractants like tributyl phosphate (TBP), tris (2-butoxyethyl) phosphate (TBEP), and tris(2-ethylhexyl) phosphate (TEHP) dissolved in n-paraffin (a mixture of C12-C14) were used as carriers. Effects of various parameters like feed acidity, carrier concentration, uranium concentration, pore size, and membrane thickness on transport of uranium were investigated. Uranium transport with different carrier solutions followed the order: TEHP ⩾ TBP > TBEP. Transport of uranium increased with feed acidity and reached a maximum at 3.3 M HNO3 and decreased thereafter with increased nitric acid concentration. The permeation of uranium across SLM increased with increased membrane pore size and decreased ...

Purification of uranium from zirconium-rich crude sodium di-uranate using counter-current solvent extraction

Solvent extraction studies on the purification of uranium from zirconium rich sodium diuranate (SDU) feed was carried out using n-tri butyl phosphate (TBP) as extractant and n-decanol as phase modifier. The presence of Zr in SDU leached solution leads to the formation of third phase during liquid–liquid extraction of uranium which was successfully prevented by addition of n-decanol in 30% (v/v) TBP/n-dodecane mixture. A seven stage counter current extraction of SDU feed solution followed by five stage stripping were carried out using optimum concentration of phase modifier 15% n-decanol-30% TBP in n-dodecane as solvent. Based on the findings a process flow-sheet has been developed for the purification of SDU to nuclear grade ammonium diuranate.