DOE OSTI2011
The current strategy for removal of cesium from the Hanford waste stream is ion-exchange using spherical Resorcinol-Formaldehyde (sRF) resin. The original resin of choice was granular SuperLig 644 resin and during testing of this resin several operational issues were identified. For example, the granular material had a high angle of internal friction resulting in fragmentation of resin particles along its edges during cycling and adverse hydraulic performance. Efforts to replace SuperLig 644 were undertaken and one candidate was the granular Resorcinol-Formaldehyde (RF) resin where experience with this cation exchanger dates back to the late 1940's. To minimize hydraulic concerns a spherical version of RF was developed and several different chemically produced batches were created. The 5E-370/641 batch of sRF was selected and for the last decade numerous studies have been performed (e.g., batch contact tests, column loading and elution tests). The Waste Treatment Plant (WTP) flowsheet shows that the aqueous phase waste stream will have a wide range of ionic concentrations (e.g., during the loading step 0-3 M free OH, 5+ M Na, 0-1 M K, 0-3 M NO{sub 3}). Several steps are required in the ion-exchange process to achieve the required Cs separation factors: loading, displacement, washing, elution, and regeneration. The sRF resin will be operated over a wide range in pH (i.e., pH of 12-14 during the loading step and pH of 0.01-1 during the elution step). During some of these steps very high levels of counter-ions and co-ions will be present within the aqueous phase. Alternative process feeds are under consideration as well (e.g., sodium levels as high as 8 M and column operation up to 45 C during loading, reduced and recycled HNO{sub 3} during elution). In order to model the performance of sRF resin through an entire ion-exchange cycle, a more robust isotherm model is required. To achieve this more robust isotherm model requires knowledge of the numbers and kinds of fixed ionogenic groups that make up sRF. Recent literature reviews and scoping titration tests strongly indicate that sRF is a polyfunctional cation exchange resin with at least three dominant types of ring groups playing a role in its isotherm behavior over the wide pH range of operations. Also three types of fixed ionogenic acid groups are present: sulfonic (SO{sub 3}H{sup -}) groups; carboxylic (COOH{sup -}) groups, and resorcylic (OH{sup -}) groups. It is this premise that we are working under in the development of a robust isotherm model for sRF over its entire planned pH operating range. The application of prototypic isotherms for modeling ion-exchange column behavior is demonstrated in Section 3 of this report. This preliminary work served to focus the development effort on the use of a mass-action based isotherm. In Section 4 of this report, the foundational material required to develop a robust isotherm model for sRF is provided. The paths taken, and choices made, are given for the reader to better understand our current status with respect to this goal and to highlight our most recent understanding of sRF exchange equilibria. Our ultimate goal is to update the CERMOD code (Aleman and Hamm, 2007) with a robust isotherm model for sRF that spans the entire pH and concentration ranges of planned operations. The isotherm model will then be used in the VERSE-LC code to model an entire ion-exchange cycle.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗