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 (K-d >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. (C) 2021 The Author(s). Published by Elsevier B.V.

Automated summary

Two novel extraction chromatography resins (ECRs) were evaluated for the uptake of Th(IV) from nitric acid feed solutions. While both resins showed high Th(IV) uptake ability, the resin with isopentyl DGA had lower uptake, especially at lower nitric acid concentrations. Kinetic modeling suggested a pseudo-second order model, while sorption isotherm studies indicated a good fitting to the Langmuir and D-R isotherm models, implying monolayer sorption and a chemisorption model.