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Title: Evaluations of Mechanisms for Pu Uptake and Retention within Spherical Resorcinol-Formaldehyde Resin Columns

Abstract

The unexpected uptake and retention of plutonium (Pu) onto columns containing spherical resorcinol-formaldehyde (sRF) resin during ion exchange testing of Cs (Cs) removal from alkaline tank waste was observed in experiments at both the Pacific Northwest National Laboratory (PNNL) and the Savannah River National Laboratory (SRNL). These observations have raised concern regarding the criticality safety of the Cs removal unit operation within the low-activity waste pretreatment system (LAWPS). Accordingly, studies have been initiated at Washington River Protection Solutions (WRPS), who manages the operations of the Hanford Site tank farms, including the LAWPS, PNNL, and elsewhere to investigate these findings. As part of these efforts, PNNL has prepared the present report to summarize the laboratory testing observations, evaluate these phenomena in light of published and unpublished technical information, and outline future laboratory testing, as deemed appropriate based on the literature studies, with the goal to elucidate the mechanisms for the observed Pu uptake and retention.

Authors:
 [1];  [1];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1365449
Report Number(s):
PNNL-25810
830403000
DOE Contract Number:
AC05-76RL01830
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES

Citation Formats

Delegard, Calvin H., Levitskaia, Tatiana G., and Fiskum, Sandra K. Evaluations of Mechanisms for Pu Uptake and Retention within Spherical Resorcinol-Formaldehyde Resin Columns. United States: N. p., 2016. Web. doi:10.2172/1365449.
Delegard, Calvin H., Levitskaia, Tatiana G., & Fiskum, Sandra K. Evaluations of Mechanisms for Pu Uptake and Retention within Spherical Resorcinol-Formaldehyde Resin Columns. United States. doi:10.2172/1365449.
Delegard, Calvin H., Levitskaia, Tatiana G., and Fiskum, Sandra K. 2016. "Evaluations of Mechanisms for Pu Uptake and Retention within Spherical Resorcinol-Formaldehyde Resin Columns". United States. doi:10.2172/1365449. https://www.osti.gov/servlets/purl/1365449.
@article{osti_1365449,
title = {Evaluations of Mechanisms for Pu Uptake and Retention within Spherical Resorcinol-Formaldehyde Resin Columns},
author = {Delegard, Calvin H. and Levitskaia, Tatiana G. and Fiskum, Sandra K.},
abstractNote = {The unexpected uptake and retention of plutonium (Pu) onto columns containing spherical resorcinol-formaldehyde (sRF) resin during ion exchange testing of Cs (Cs) removal from alkaline tank waste was observed in experiments at both the Pacific Northwest National Laboratory (PNNL) and the Savannah River National Laboratory (SRNL). These observations have raised concern regarding the criticality safety of the Cs removal unit operation within the low-activity waste pretreatment system (LAWPS). Accordingly, studies have been initiated at Washington River Protection Solutions (WRPS), who manages the operations of the Hanford Site tank farms, including the LAWPS, PNNL, and elsewhere to investigate these findings. As part of these efforts, PNNL has prepared the present report to summarize the laboratory testing observations, evaluate these phenomena in light of published and unpublished technical information, and outline future laboratory testing, as deemed appropriate based on the literature studies, with the goal to elucidate the mechanisms for the observed Pu uptake and retention.},
doi = {10.2172/1365449},
journal = {},
number = ,
volume = ,
place = {United States},
year = 2016,
month = 9
}

Technical Report:

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  • Bechtel National, Inc. (BNI) is evaluating the alternate Cs ion exchanger, spherical resorcinol-formaldehyde (RF), for use in the River Protection Project-Waste Treatment Plant (RPP-WTP).( ) Previous test activities with spherical RF indicate that it has adequate capacity, selectivity, and kinetics to perform in the plant according to the flowsheet needs. It appears to have better elution and hydraulic properties than the existing alternatives: ground-gel RF and SuperLig® 644 (SL 644).( ) To date, the spherical RF performance testing has been conducted on freshly manufactured resin (within ~2 months of manufacture). The ion exchange resins will be manufactured and shipped tomore » the WTP up to 1 year before being used in the plant. Changes in the resin properties during storage could reduce the capacity of the resin to remove Cs from low-activity waste solutions. Active sites on organic SL-644 resin have been shown to degrade during storage (Arm et al. 2004). Additional testing was needed to study the effects of storage conditions and aging on spherical RF ion exchange performance. Variables that could have a significant impact on ion exchange resins during storage include storage temperature, medium, and time. Battelle—Pacific Northwest Division (PNWD) was contracted to test the effects of various storage conditions on spherical RF resin. Data obtained from the testing will be used by the WTP operations to provide direction for suitable storage conditions and manage the spherical RF resin stock. Storage test conditions included wet and dry resin configurations under nitrogen at three temperatures. Work was initially conducted under contract number 24590-101-TSA-W000-00004 satisfying the needs defined in Appendix C of the Research and Technology Plan( ) TSS A-219 to evaluate the impact of storage conditions on RF resin performance. In February 2007, the contract mechanism was switched to Pacific Northwest National Laboratory (PNNL) Operating Contract DE-AC05-76RL01830.« less
  • A small-column ion exchange (SCIX) system has been proposed for removing cesium from the supernate and dissolved salt solutions in the high-level-waste tanks at the Savannah River Site (SRS). The SCIX system could use either crystalline silicotitanate (CST), an inorganic, non-regenerable sorbent, or spherical resorcinol-formaldehyde (RF), a new regenerable resin, to remove cesium from the waste solutions. The baseline method for eluting the cesium from the RF resin uses 15 bed volumes (BV) of 0.5 M nitric acid (HNO{sub 3}). The nitric acid eluate, containing the radioactive cesium, would be combined with the sludge from the waste tanks and wouldmore » be converted into glass at the Defense Waste Processing Facility (DWPF) at SRS. The amount of nitric acid that would be used to elute the RF resin, using the current elution protocol, exceeds the capacity of DWPF to destroy the nitrate ions and maintain the required chemical reducing environment in the glass melt. Installing a denitration evaporator at SRS is technically feasible but would add considerable cost to the project. Alternate methods for eluting the resin have been tested, including using lower concentrations of nitric acid, other acids, and changing the flow regimes. About 4 BV of 0.5 M HNO{sub 3} are required to remove the sodium (titrate the resin) and most of the cesium from the resin, so the bulk of the acid used for the baseline elution method removes a very small quantity of cesium from the resin. A summary of the elution methods that have been tested are listed.« less
  • A small column ion exchange (SCIX) system has been proposed for removal of cesium from caustic, supernatant, and dissolved salt solutions stored or generated from high-level tank wastes at the US Department of Energy (DOE) Hanford Site and Savannah River Sites. In both instances, deployment of SCIX systems, either in-tank or near-tank, is a means of expediting waste pretreatment and dispositioning with minimal or no new infrastructure requirements. Conceptually, the treatment approach can utilize a range of ion exchange media. Previously, both crystalline silicotitanate (CST), an inorganic, nonelutable sorbent, and resorcinol-formaldehyde (RF), an organic, elutable resin, have been considered formore » cesium removal from tank waste. More recently, Pacific Northwest National Laboratory (PNNL) evaluated use of SuperLig{reg_sign} 644, an elutable ion exchange medium, for the subject application. Results of testing indicate hydraulic limitations of the SuperLig{reg_sign} resin, specifically a high pressure drop through packed ion exchange columns. This limitation is likely the result of swelling and shrinkage of the irregularly shaped (granular) resin during repeated conversions between sodium and hydrogen forms as the resin is first loaded then eluted. It is anticipated that a similar flow limitation would exist in columns packed with conventional, granular RF resin. However, use of spherical RF resin is a likely means of mitigating processing limitations due to excessive pressure drop. Although size changes occur as the spherical resin is cycled through loading and elution operations, the geometry of the resin is expected to effectively mitigate the close packing that leads to high pressure drops across ion exchange columns. Multiple evaluations have been performed to determine the feasibility of using spherical RF resin and to obtain data necessary for design of an SCIX process. The work performed consisted of examination of radiation effects on resin performance, quantification of cesium adsorption performance as a function of operating temperature and pH, and evaluation of sodium uptake (titration) as function of pH and counteranion concentration. The results of these efforts are presented in this report. Hydraulic performance of the resin and the use of eluant alternatives to nitric acid have also been evaluated and have been reported elsewhere (Taylor 2009, Taylor and Johnson 2009).« less
  • This report presents characterization data for two spherical resorcinol-formaldehyde (sRF) resin beds that had processed cesium in non-radioactive and radioactive cycles. All column cycle operations for the resin beds including loading, displacements, elution, regeneration, breakthroughs, and solution analyses are reported in Nash and Duignan, 2009a. That report covered four ion exchange (IX) campaigns using the two {approx}11 mL beds in columns in a lead-lag arrangement. The first two campaigns used Savannah River Site (SRS) Tank 2F nonradioactive simulant while the latter two were fed with actual dissolved salt in the Savannah River National Laboratory (SRNL) Shielded Cells. Both radioactive cyclesmore » ran to cesium breakthrough of the lead column. The resin beds saw in excess of 400 bed volumes of feed in each cycle. Resin disposal plans in tank farm processing depend on characterizations of resin used with actual tank feed. Following a final 30 bed volume (BV) elution with nitric acid, the resin beds were found to contain detectable chromium, barium, boron, aluminum, iron, sodium, sulfur, plutonium, cesium, and mercury. Resin affinity for plutonium is important in criticality safety considerations. Cesium-137 was found to be less than 10E+7 dpm/g of resin, similar to past work with sRF resin. Sulfur levels are reasonably consistent with other work and are expected to represent sulfur chemistry used in the resin manufacture. There were low but detectable levels of technetium, americium, and curium. Toxicity Characteristic Leaching Procedure (TCLP) work on the used (eluted) resin samples showed significant contents of mercury, barium, and chromium. One resin sample exceeded the TCLP level for mercury while the other metals were below TCLP levels. TCLP organics measurements indicated measurable benzene in one case, though the source was unknown. Results of this work were compared with other work on similar sRF resin characterizations in this report. This is the first work to quantify mercury on sRF resin. Resin mercury content is important in plans for the disposition of used sRF resin. Mercury speciation in high level waste (HLW) is unknown. It may be partly organic, one example being methyl mercury cation. Further study of the resin's affinity for mercury is recommended.« less
  • This report presents data on batch contact and column testing tasks for spherical resorcinol-formaldehyde (sRF) resin. The testing used a non-radioactive simulant of SRS Tank 2F dissolved salt, as well as an actual radioactive waste sample of similar composition, which are both notably high in sodium (6 M). The resin was Microbeads batch 5E-370/641 which had been made on the hundred gallon scale. Equilibrium batch contact work focused on cesium at a temperature of 25 C due to the lack of such data to better benchmark existing isotherm models. Two campaigns were performed with small-scale ion exchange columns, first withmore » Tank 2F simulant, then with actual dissolved salt in the Shielded Cells. An extrapolation of the batch contact results with radioactive waste over-predicted the cesium loaded onto the IX sRF resin bed by approximately 11%. This difference is not unexpected considering uncertainties from measurement and extrapolation and because the ion exchange that occurs when waste flows through a resin bed probably cannot reach the same level of equilibrium as when waste and resin are joined in a long term batch contact. Resin was also characterized to better understand basic chemistry issues such as holdup of trace transition metals present in the waste feed streams. The column tests involved using two beds of sRF resin in series, with the first bed referred to as the Lead column and the second bed as the Lag column. The test matrix included two complete IX cycles for both the simulant and actual waste phases. A cycle involves cesium adsorption, until the resin in the Lead column reaches saturation, and then regenerating the sRF resin, which includes eluting the cesium. Both the simulated and the actual wastes were treated with two cycles of operation, and the resin beds that were used in the Lead and Lag columns of simulant test phase were regenerated and reused in the actual waste test phase. This task is the first to demonstrate the treatment of SRS waste with sRF resin and the tests clearly demonstrated cesium decontamination for actual waste. The results of the column tests were similar for both the simulated and the actual waste and demonstrated Cs removal with sRF from both wastes. For a flowrate of 1.4 bed volumes (BV)/hour at 25 C those results with sRF resin were: (1) Simulant and actual waste results are equivalent; (2) Cs breakthrough began between 200 and 250 BV; (3) Cs breakthrough reached 100% at around 400 BV; (4) Cs breakthrough curve from 5% to 100% is approximately linear; (5) Cs elution with 0.5 M HNO3 starts at 2 BV and ends at 6BV; (6) Most, if not all, of Cs adsorbed during treatment is released during elution; (7) At 100% breakthrough of Cs the resin bed adsorbs approximately 85% of full capacity before detection in the effluent; the remaining 15% is adsorbed at saturation; (8) Approximately 90% of resin bed changes (color and volume) are complete by 6 BV; and (9) During elution the resin shrinks to about 80% of its fully working (sodium form) BV.« less