Urea and thiourea have been successfully deposited at the surface of silica beads (through one-pot reaction with formaldehyde) for designing new sorbents for U(VI) and Th(IV) recovery (UR/SiO2 and TUR/SiO2 composites, respectively). These materials have been characterized by FTIR, titration, elemental analysis, BET, TGA, SEM-EDX for identification of structural and chemical properties, and interpretation of binding mechanisms. Based on deprotonation of reactive groups (amine, carbonyl, or thiocarbonyl) and metal speciation, the optimum pH was ~4. Uptake kinetics was fast (equilibrium within 60-90 min). Although the kinetic profiles are fitted by the pseudo-first order rate equation, the resistance to intraparticle diffusion cannot be neglected. Sorption isotherms were fitted by Langmuir equation (maximum sorption capacities: 1-1.2 mmol g-1). Thermodynamics are also investigated showing differences between the two types of functionalized groups: exothermic for TUR/SiO2 and endothermic for UR/SiO2. Metal desorption is highly effective using 0.3-0.5 M HCl solutions: total desorption occurs within 30-60 min; sorption/desorption properties are remarkably stable for at least 5 cycles. The sorbents have marked preference for U(VI) and Th(IV) over alkali-earth and base metals at pHeq ~4.8. By preliminary precipitation steps, it is possible "cleaning" ore leachates of pegmatite ore, and recovering U(VI) and Th(IV) using functionalized silica beads. After elution and selective recovery by precipitation with oxalate (Th-cake) and alkaline (U-cake), the metals can be valorized.
Keywords: Application to acidic leachates; Selectivity issues; Sorption kinetics and isotherms; Uranium and thorium sorption and desorption; Urea and thiourea functionalization of silica beads.
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