Chromatographic separation of platinum group metals from simulated high level liquid waste using macroporous silica-based adsorbents.
To separate platinum group metals (PGMs) from high level liquid waste, three novel macroporous silica-based adsorbents, namely, (Crea+Dodec)/SiO2-P, (Crea+TOA)/SiO2-P and (MOTDGA+TOA)/SiO2-P, were synthesized by introducing extractants Crea (N',N'-di-n-hexyl-thiodiglycolamide), TOA (Tri-n-octylamine), MOTDGA (N,N'-dimethyl-N,N'-di-n-octyl-thiodiglycolamide) along with theirs modifier, Dodec (n-dodecyl alcohol), into 50μm diameter SiO2-P particles by impregnation. Chromatographic separation of PGMs from simulated high level liquid waste was investigated by column method. It was found that 100% of Pd(II) and Re(VII) could be eluted out from simulate HLLW in 3.0M HNO3 solution using three adsorbents. For Ru(III) and Rh(III), high temperature has distinct effect on the adsorption rate and a further study for Ru(III) and Rh(III) is necessary to separate them from HLLW completely. In all six column experiments, a relatively satisfactory chromatographic separation operating for PGMs from simulated HLLW was obtained using (Crea+TOA)/SiO2-P adsorbent packed column at 323K.
N,N,N′,N′-Tetra(2-Ethylhexyl) Thiodiglycolamide T(2EH)TDGA: A Promising Ligand for Separation and Recovery of Palladium from High Level Liquid Waste (HLLW) Solutions
The extraction properties of N,N,N′,N′-tetra(2-ethylhexyl)thiodiglycolamide T(2EH)TDGA have been evaluated for the separation and recovery of palladium from simulated high-level liquid waste (SHLW). T(2EH)TDGA has shown very high selectivity for Pd (II) over other metal ions present in SHLW. The separation factor (SF) for Pd (II) over other metal ions was found to be more than 105. Reusability studies of the extractant indicate that DPd remained almost constant even after five successive cycles of extraction and stripping. Palladium was quantitatively recovered from thiourea strip solution by treating it with ammonia and filtering the precipitate of palladium sulphide. The acid uptake constant (KH) was found to be 0.62 which could be due to the presence of two carbonyl groups of amidic moiety. To account for very high extractability of palladium with T(2EH)TDGA over other ‘S’ donor extractants, namely Bis-(2-ethylhexyl)sulphoxide (BESO), FTIR, as well as Raman studies were carried out. FTIR and Raman studies suggested the ligation through carbonyl as well as the thio-ether group. Conditional extraction constants (log K′ex) were determined and the thermodynamic parameters were calculated from the dependence of the conditional extraction constant (log K′ex) on temperature. The calculated values of ΔGex, ΔHex, and ΔSex were −41.78 kJmol−1, −55.12 kJmol−1 and −44.04 JK−1 mol−1 respectively. The extraction process is indicated to be enthalpy driven with the entropy factor counteracting it.
The role of dissolved oxygen in supercritical water in the oxidation of ferritic–martensitic steel
Abstract To assess the role of dissolved oxygen in supercritical water on the growth processes of oxide scales, a marker experiment of ferritic–martensitic steel was performed by exposing to supercritical water (H 2 16 O) containing marked 18 O 2 at 600 °C under 25 MPa. The oxide scale was analysed by using Secondary Ion Mass Spectrometry (SIMS). The oxygen isotope profile shows that dissolved oxygen and supercritical water react with metals simultaneously. Dissolved oxygen changes the oxidation/reduction potential of supercritical water leading to an increase in the oxidation rate. The oxidation rate increases with increase in dissolved oxygen content in supercritical water. The mechanism of the effect of dissolved oxygen on oxidation is discussed.