A comparative study on the uptake of lanthanides from acidic feeds using extraction chromatography resins containing N,N,N',N'-tetra-n-alkyl diglycolamides with varying alkyl chain lengths in an ionic liquid.

A comparative study on the uptake of several rare earth element (REE) ions viz. La(III), Ce(III), Pr(III), Nd(III), Sm(III), Gd(III) and Dy(III) was carried out from nitric acid feeds using four extraction chromatography resins which contained the diglycolamide (DGA) ligands, N,N,N',N'-tetra-n-alkyldiglycolamide with n-pentyl (TPDGA), n-hexyl (THDGA), n-octyl (TODGA) and n-decyl (TDDGA) groups taken in a room temperature ionic liquid (C4mim·NTf2). The uptake of the lanthanides followed the trend: La(III) < Ce(III) < Pr(III) < Nd(III) < Sm(III) < Gd(III) < Dy(III), which is similar to their ionic potential values and the uptake trend of the resins was TPDGA > THDGA > TODGA > TDDGA. The uptake of the metal ions was very high (>104 g/mL) for all the lanthanide ions and was found to increase with increasing nitric acid concentrations. Based on the encouraging batch data, column studies were carried out with all the four extraction chromatography resins with the lanthanide ions used in this work. The column studies were carried out with both individual lanthanide ions and their mixtures. While the loading studies were carried out with 80 mg/L solutions of the metal ions (with respect to each of those) in the mixture of REEs, the elution studies were carried out using a solution of 0.05 M EDTA in 1 M guanidine carbonate. For the column studies involving individual REEs, 550 mg/L solutions were used. The elution profiles appeared to be sharp as >95% elution of the metal ions was accomplished in only 3 mL of the eluent which amounted to only 1.6 bed volumes which is highly impressive. When the studies were carried out with the mixture of the lanthanide ions, the breakthrough of Dy(III) was last while that of La(III) was seen at much lower volumes which was dependent on the nature of the extractant in the resins.

Radiation stability of two extraction chromatography resin materials containing substituted diglycolamide ligands in an ionic liquid.

The radiation stability of two extraction chromatography resins containing diglycolamide ligands viz. TPDGA (N,N,N',N'-tetra-n-pentyl diglycolamide) and TODGA (N,N,N',N'-tetra-n-octyl diglycolamide) in a room temperature ionic liquid (C4mim.NTf2) was studied by exposing to gamma rays from a 60Co source. The resins were irradiated to varying gamma ray dose up to 1000 kGy where both the dry resins and wet resins (containing a fixed amount nitric acid in contact) were used. The performance assessment of the resins was done by physicochemical characterization as well as uptake studies; both by batch as well as column methods. The physicochemical characterization of the resins was done using FTIR analysis while the surface morphology of the resins was carried out by scanning electron microscopy. The uptake of the metal ions, typically that of Am(III) and Eu(III), representing the trivalent actinides and lanthanides was studied by batch method. The dry resins and those in contact with nitric acid yielded nearly identical results suggesting minimal effect of the radiolytic products of nitric acid on the resin performance. There was negligible change in the Kd values up to an absorbed dose of 300 kGy beyond which there was sharp decrease. However, the Kd values were still quite large even after an absorbed dose of 1000 kGy. The column performance of the irradiated resins was also assessed by the uptake and elution of Eu(III) ion and though loading was affected, the elution behavior was found to have insignificant effect.

Stability of composite polymeric beads containing a calix[4]arene-mono-crown-6 ligand for radio-cesium separation.

Bis-octyloxy-calix[4]arene-mono-crown-6 (BOCMC) is a selective ligand for Cs(I) cation, and has been used in solvent extraction method for its separation from acidic feed. Looking at the various advantages and ease of extraction chromatography separation method, an attempt was made to prepare stable composite beads containing BOCMC entrapped in a suitable polymeric matrix. Therefore, an attempt was made to prepare a series of composite polymeric beads containing BOCMC in polysulfone (PS), polyether sulfone (PES) and sodium alginate polymeric matrix. Preparations of the beads were attempted by dissolving the solid BOCMC in the polymer solution, and also by using the ligand solution in isodecanol/dodecane and ionic liquids and then mixing in the polymeric solution. Every attempt failed to get the desired quality of beads in PES and sodium alginate matrix. However, very good quality and stable beads were obtained when 25 mM ligand solution dissolved in C8mim.Tf2N ionic liquid was used in PS matrix. Detail study for the extraction chromatography separation of Cs(I) was studied with BOCMC/C8mim.Tf2N/PS composite beads. Detail investigations on the preparation, characterization, reusability and radiation stability of these beads have been studied and reported in details.

Selective uptake of thorium(IV) from nitric acid medium using two extraction chromatographic resins based on diglycolamide-calix[4]arenes: Application to thorium-uranyl separation in an actual sample.

Two novel extraction chromatography resins (ECRs) containing two diglycolamide (DGA) -functionalized calix[4]arenes with n-propyl and isopentyl substituents at the amide nitrogen atom, termed as ECR-1 and ECR-2, respectively, were evaluated for the uptake of Th(IV) from nitric acid feed solutions. While both the resins were having a quite high Th(IV) uptake ability (Kd >3000 at 3 M HNO3), the uptake was relatively lower with the resin containing the isopentyl DGA, which appeared magnified at lower nitric acid concentrations. Kinetic modeling of the sorption data suggested fitting to the pseudo-second order model pointing to a chemical reaction during the uptake of the metal ion. Sorption isotherm studies were carried out showing a good fitting to the Langmuir and D-R isotherm models, suggesting the uptake conforming to monolayer sorption and a chemisorption model. Glass columns with a bed volume of ca. 2.5 mL containing ca. 0.5 g lots of the ECRs were used for studies to assess the possibility of actual applications of the ECRs. Breakthrough profiles obtained with feed containing 0.7 g/L Th(NO3)3 solution resulted in breakthrough volumes of 8 and 5 mL, respectively, for the ECR-1 and ECR-2 resins. Near quantitative elution of the loaded metal ion was possible using a solution of oxalic acid and nitric acid. A method for the separation of Th-234 from natural uranium was demonstrated for the possible application of ECR-1.

Two novel extraction chromatographic resins containing benzene-centered tripodal diglycolamide ligands: Actinide uptake, kinetic modeling and isotherm studies.

Two novel extraction chromatographic resins (EC), termed as RL-1 and RL-2, were prepared by impregnating two benzene-centered tripodal iglycolamide ligands (Bz-T-DGA) containing different spacer groups where the ligands are termed as L-1 and L-2, respectively. They were employed for the uptake of actinide and fission product ions, viz. Am3+, Eu3+, UO22+, Np4+, Pu4+, Sr2+, and Cs+, from acidic feeds. Weight distribution coefficient (Kd) values were measured by the batch method and the loaded metal ions were back extracted using a 0.01 M EDTA solution at pH 4. Kinetic modeling of the sorption data of Am(III) on both resins suggested pseudo-second order rate kinetics with rate constants of 1.68 × 10-6 and 2.47 × 10-6 g/cpm.min for the resins containing L-1 and L-2, respectively. Sorption isotherm studies indicated the Langmuir monolayer chemisorption phenomenon with Eu(III) experimentally determined saturation uptake capacities of 6.02 ± 0.11 and 5.49 ± 0.14 mg per g of RL-1 and RL-2 resins, respectively. As the batch uptake study results appeared encouraging, column studies were also carried out using both resins. The resin reusability data indicated a marginal change in the Kd values for the RL-1 resin up to three repeat runs beyond which a steady decrease of the Kd value was seen. On the other hand, in the case of RL-2 a steady decrease in the Kd values was observed for three repeat runs beyond which there was marginal change.