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Title: An investigation of the radiolytic stability of a resorcinol-formaldehyde ion exchange resin

Abstract

Developing and demonstrating waste separations technologies are the principal objectives of the Underground Storage Tank -Integrated Demonstration (UST-ID) Program carried out by Pacific Northwest Laboratories (PNL) at the DOE Hanford site. One planned separation technique utilizes ion exchange for removal of cesium and strontium from high-level liquid supernates. A resorcinol-formaldehyde resin, which is a polycondensation-type cation exchange resin for cesium removal, has been developed at the Savannah River Technology Center (SRTC) and has demonstrated superlative performance in testing at SRS, Oak Ridge and PNL. Advantages of this resin relative to other media for cesium removal are its high capacity for cesium and its compatibility with the high pH and aluminum and sodium concentrations of both Hanford and SRS high-level liquid wastes.

Authors:
;
Publication Date:
Research Org.:
Westinghouse Savannah River Co., Aiken, SC (United States)
Sponsoring Org.:
USDOE, Washington, DC (United States)
OSTI Identifier:
10136677
Report Number(s):
WSRC-RP-94-148
ON: DE94009113
DOE Contract Number:
AC09-89SR18035
Resource Type:
Technical Report
Resource Relation:
Other Information: PBD: 31 Jan 1994
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; SAVANNAH RIVER PLANT; RADIOACTIVE WASTE PROCESSING; HIGH-LEVEL RADIOACTIVE WASTES; SEPARATION PROCESSES; RESINS; RADIOLYSIS; CESIUM; STRONTIUM; ION EXCHANGE; TANKS; RESORCINOL; FORMALDEHYDE; WATER; LEACHING; 052001; 400105; WASTE PROCESSING; SEPARATION PROCEDURES

Citation Formats

Crawford, C.L., and Bibler, N.E. An investigation of the radiolytic stability of a resorcinol-formaldehyde ion exchange resin. United States: N. p., 1994. Web. doi:10.2172/10136677.
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Crawford, C.L., & Bibler, N.E. An investigation of the radiolytic stability of a resorcinol-formaldehyde ion exchange resin. United States. doi:10.2172/10136677.
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Crawford, C.L., and Bibler, N.E. Mon . "An investigation of the radiolytic stability of a resorcinol-formaldehyde ion exchange resin". United States. doi:10.2172/10136677. https://www.osti.gov/servlets/purl/10136677.
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@article{osti_10136677,
title = {An investigation of the radiolytic stability of a resorcinol-formaldehyde ion exchange resin},
author = {Crawford, C.L. and Bibler, N.E.},
abstractNote = {Developing and demonstrating waste separations technologies are the principal objectives of the Underground Storage Tank -Integrated Demonstration (UST-ID) Program carried out by Pacific Northwest Laboratories (PNL) at the DOE Hanford site. One planned separation technique utilizes ion exchange for removal of cesium and strontium from high-level liquid supernates. A resorcinol-formaldehyde resin, which is a polycondensation-type cation exchange resin for cesium removal, has been developed at the Savannah River Technology Center (SRTC) and has demonstrated superlative performance in testing at SRS, Oak Ridge and PNL. Advantages of this resin relative to other media for cesium removal are its high capacity for cesium and its compatibility with the high pH and aluminum and sodium concentrations of both Hanford and SRS high-level liquid wastes.},
doi = {10.2172/10136677},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Mon Jan 31 00:00:00 EST 1994},
month = {Mon Jan 31 00:00:00 EST 1994}
}
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Technical Report:
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DOI:  10.2172/10136677
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  • ; ;
    Radiolytic stability of a resorcinol-formaldehyde polycondensation-type cation exchange resin was investigated for up to lE09 rads total dose. The resorcinol-formaldehyde resin is a resin that has potential cesium decontamination applications at Pacific Northwest and Savannah River. We have determined both radiation and storage effects on performance of the resin using 101-AW Hanford simulant and ASTM Type-I water. Distribution coefficient determinations, total carbon analysis, and physical observations lead us to conclude that radiation up to lE08 rads does not significantly affect the performance of the resin. The resin is more stable to radiation in water than in 101-AW Hanford simulant. Alsomore » radiation or storage does not affect the thermal stability of the resin. Gas production rates for several resin slurries increased in the order of resin/101-AW Hanford simulant, resin/ASTM water, and resin/0.5 M HNO{sub 3}. H{sub 2} is produced from radiolysis of resin in 101-AW Hanford simulant with a G value of G(H{sub 2}) of 0.11 {plus_minus} 0.02 molecules/100eV and in 0.5 M HNO{sub 3} with a G value of G(H{sub 2}) of 0.27 {plus_minus} 0.02 molecules/lOOeV.« less

  • ; ; ; ...
    The 177 underground storage tanks at the DOE`s Hanford Site contain an estimated 180 million tons of high-level radioactive wastes. It is desirable to remove and concentrate the highly radioactive fraction of the tank wastes for vitrification. Resorcinol-formaldehyde (R-F) resin, an organic ion-exchange resin with high selectivity and capacity for the cesium ion, which is a candidate ion-exchange material for use in remediation of tank wastes. The report includes information on the structure/function analysis of R-F resin and the synthetic factors that affect performance of the resin. CS-100, a commercially available phenol-formaldehyde (P-F) resin, and currently the baseline ion-exchanger formore » removal of cesium ion at Hanford, is compared with the R-F resin. The primary structural unit of the R-F resin was determined to consist of a 1,2,3,4-tetrasubstituted resorcinol ring unit while CS-100, was composed mainly of a 1,2,4-trisubstituted ring. CS-100 shows the presence of phenoxy-ether groups, and this may account for the much lower decontamination factor of CS-100 for cesium ion. Curing temperatures for the R-F resin were found to be optimal at 105--130C. At lower temperatures, insufficient curing, hence crosslinking, of the polymer resin occurs and selectivity for cesium drops. Curing at elevated temperatures leads to chemical degradation. Optimal particle size for R-F resin is in the range of 20--50 mesh-sized particles. R-F resin undergoes chemical degradation or oxidation which destroys ion-exchange sites. The ion-exchange sites (hydroxyl groups) are converted to quinones and ketones. CS-100, though it has much lower performance for cesium ion-exchange, is significantly more chemically stable than R-F resin. To gamma radiation, CS-100 is more radiolytically stable than R-F resin.« less

  • The expected performance of an alternative ion exchange resin, i.e., Resorcinol-Formaldehyde for the removal of cesium from Hanford high level radioactive alkaline waste is discussed. The SuperLig(R) 644 resin is the current primary resin of choice. A consistent performance comparison between RF and SuperLig(R) 644 resins is also provided. This report represents an initial report on our ability and knowledge with regard to modeling the RF resin ion exchange system, i.e., RF in its spherical bead structure. Only the loading phase of the cycle process is addressed within this report. Pertinent bench-scale column tests and batch equilibrium experiments are addressed.more » The methodology employed and sensitivity analyses are also discussed, i.e., the existing methodology employed for SuperLig(R) 644 resin analyses is also employed for the RF resin analyses. Pilot-scale testing is not assessed since no pilot-scale testing was available or planned at the time of this report, i.e., only Stage 1 activities are covered. Column performance predictions are made considering three selected feed compositions under nominal operating conditions. The sensitivity analyses provided help to identify key parameters that aid in resin procurement acceptance criteria. The methodology and application presented within this report reflect the expected behavior of RF resin manufactured at the small-scale, i.e., approximately 250 ml batch size level by Sintef. No analysis associated with the original ground RF resin is presented within this report. WTP decided that the baseline RF resin should be changed to the spherical bead form.« less

  • ; ; ; ...
    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

  • ;
    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