Extractants radiolytic degradation

TBP is a sufficiently powerful extractant for actinides that it may be used in diluted form. Dilution improves the hydrodynamic properties of the solvent, allowing more complete and rapid phase disengagement. Typically concentrations of 20-30 v/o TBP in OK are used in process flowsheets. Although TBP is relatively stable as an extractant, radiolysis does lead to the formation of some acidic phosphate esters, HDBP and H2MBP, which can impair process performance.289 An aqueous alkali wash of the recycled solvent is usually carried out to remove those by products. Radiolytic degradation of the diluent in the presence of nitric acid can result in the formation of hydroxamic acids,290 which can lead to fission product retention by the organic phase. Again the solvent wash is used to prevent the accumulation of such species. A comprehensive account of the industrial utilization of TBP has recently been published.291... 

Berthon, L., Morel, J.M., Zorz, N. et al. 2001. DIAMEX process for minor actinide partitioning Hydrolytic and radiolytic degradations of malonamide extractants. Sep. Sci. Technol. 36 (5 6) 709-728. 

Hydrolytic and radiolytic degradation of TAP solution in normal paraffinic hydrocarbon (NPH) in the presence of nitric acid was investigated. Physicochemical properties such as density, viscosity, and phase-disengagement time (PDT) were measured for undegraded and degraded solutions (197). The variations in these parameters were not very different from those obtained with degraded TBP. Thus, the hydro-dynamic problems expected during the solvent-extraction process with TAP would be similar to those encountered with TBP/NPH system. The influence of chemical... 

Since the pioneering work of Siddall, /V./V-dialkyl amides have been evaluated extensively as alternative extractants to TBP (200, 201). The salient features of amides as extractants are (i) low volume of secondary waste generated (completely incinerable), (ii) innocuous nature of chemical and radiolytic degradation products (better decontamination from fission products andregeneration/clean up easier), (iii) low aqueous-phase solubility, (iv) final U and Pu products streams are free of P contamination, and (v) ease of synthesis. However, LOC values of U and Pu as well as viscosity are... 

Di(2-ethylhexyl) phosphoric acid (HDEHP) is an extractant molecule used for An(III)/Ln(III) separation. Used in TALSPEAK-type processes in a mixture with TBP, or in the DIAMEX-SANEX process in a mixture with a malonamide (154-157), it has also been proposed, in a mixture with TBP, to remove strontium from PUREX acid waste solution in the Hanford B plant (158). Therefore, numerous studies have focussed on the radiolytic degradation of HDEHP and its effects on the extraction of Sr(II), lanthanides(III), and actinides(III) (10, 158-163). 

Extraction of U(VI) and Pu(IV) from 1 to 8 mol L 1 HN03 solutions by radiolytically degraded DCH18C6 in toluene was studied (256). A decrease in the distribution ratios for both U and Pu was observed for irradiation in the range 0.010-0.071 MGy, with a higher effect for Pu(IV). For 0.2 mol I. DCH18C6-toluene solution in contact with 3 mol I. nitric acid, D, decreased from 0.21 to 0.12 and /.)hl from 64.3 to 6.42 after a dose of 0.07 MGy. This behavior was explained by both diluent and extractant degradation. 

To limit the radiolytic degradation of extractants, the influences of free-radical inhibitors have been measured. The addition of dimethoxybenzaldehydes (DMBA), particularly 3,5- and 3,4-DMBA, to the PUREX solvent could improve its stability and decrease its contamination (307). DMBA has a double effect, including a protective effect for the excited molecules of TBP (because of its low ionization potential), and the aldehyde radiolysis products could react with the HDBP present and therefore inhibit its complexing properties. 

The selection of a suitable diluent is important to limit radiolytic degradation. Diluents currently used in nuclear applications are hydrocarbons, despite their well-known sensitization effect on radiolysis, as mentioned for alkylphosphates or amide extractants (90, 182, 183, 199), and as discussed in Section 8.4.2. To avoid this negative effect or to enhance the solubility of ligands and metallic complexes, other diluents have been selected and their influence on degradation investigated. 

The most stable are the macrocyclic extractants, with radiolytic degradation yields lower than 1 molecule/100 eV (7), and especially the calix-arenes G(-calixarene) <0.1 (72) ... 

Nowak, Z. 1977. Radiolytic degradation of extractant-diluent systems used in the PUREX process. Nukleonika 22 155-171. 

The radiolytic and chemical degradation of TBP gives rise to monobu-tylphosphoric acid (MBP) and DBP, which are powerful extractants under low acidic conditions. As stripping in the PUREX process is carried out under such... 

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