Alternatives to nitric acid stripping in the caustic-side solvent extraction (CSSX) process for cesium removal from alkaline high-level waste

Effective alternatives to nitric acid stripping in the Caustic-Side Solvent Extraction (CSSX) solvent have been demonstrated in this work. The CSSX solvent employs calix[4]arene-bis(tert-octylbenzo-18-crown-6) (BOBCalixC6) as the cesium extractant in a modified alkane diluent for decontamination of alkaline high-level wastes, such as those found at the Savannah River and Hanford sites. Results reported in this paper support the idea that replacement of the nitrate anion by a much more hydrophilic anion like borate can substantially lower cesium distribution ratios on stripping. Without any other change in the CSSX flowsheet, however, the use of a boric acid stripping solution in place of the 1 mM nitric acid solution used in the CSSX process marginally, though perhaps still usefully, improves stripping. The less-than-expected improvement was explained by the carryover of nitrate from scrubbing into stripping. Accordingly, more effective stripping is obtained after a scrub of the solvent with 0.1 M sodium hydroxide. Functional alternatives to boric acid include sodium bicarbonate or cesium hydroxide as strip solutions. Profound stripping improvement is achieved when trioctylamine, one of the components of the CSSX solvent, is replaced with a commercial guanidine reagent (LIX® 79). The more basic guanidine affords greater latitude in the selection of aqueous conditions in that it becomes protonated even at mildly alkaline pH values. Under process-relevant conditions, cesium distribution ratios on stripping are approximately 100-fold lower compared with the current CSSX performance. The tolerance to surfactants is good, and the extraction properties of the solvent remain unchanged over three successive extract-scrub-strip cycles. From the point of view of compatibility with downstream processing, boric acid represents an attractive stripping agent, as it is also a potentially ideal feed for borosilicate vitrification of the separated 137Cs product stream. The possibilities for use of these results toward a dramatically better next-generation CSSX process, possibly one employing the more soluble cesium extractant calix[4]arene-bis(2-ethylhexylbenzo-18-crown-6) (BEHBCalixC6) are discussed.