Download or read book Literature Review of Spherical Resorcinol Formaldehyde for Cesium Ion Exchange written by and published by . This book was released on 2014 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: The current report summarizes work performed throughout the scientific community and DOE complex as reported in the open literature and DOE-sponsored reports to evaluate the Cs+ ion exchange (CIX) characteristics of SRF resin. King (2007) completed a similar literature review in support of material selection for the Small Column Ion Exchange (SCIX) project. Josephson et al. (2010) and Sams et al. (2009) provided a similar brief review of SRF CIX for the near-tank Cs+ removal (NTCR) project. Thorson (2008a) documented the basis for recommending SRF over SuperLigTM 644 as the primary CIX resin in the WTP. The current review expands on previous work, summarizes additional work completed to date, and provides a broad view of the literature without focusing on a specific column system. Although the focus of the current review is the SRF resin, many cited references include multiple materials such as the non-spherical GGRF and SuperLigTM 644 organic resins and crystalline silicotitanate (CST) IONSIVTM IE-911, a non-elutable inorganic material. This report summarizes relevant information provided in the literature.

Download or read book Small Column Cesium Ion Exchange Elution Testing of Spherical Resorcinol Formaldehyde written by and published by . This book was released on 2011 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This report summarizes the work performed to evaluate multiple, cesium loading, and elution cycles for small columns containing SRF resin using a simple, high-level waste (HLW) simulant. Cesium ion exchange loading and elution curves were generated for a nominal 5 M Na, 2.4E-05 M Cs, 0.115 M Al loading solution traced with 134Cs followed by elution with variable HNO3 (0.02, 0.07, 0.15, 0.23, and 0.28 M) containing variable CsNO3 (5.0E-09, 5.0E-08, and 5.0E-07 M) and traced with 137Cs. The ion exchange system consisted of a pump, tubing, process solutions, and a single, small (≈15.7 mL) bed of SRF resin with a water-jacketed column for temperature-control. The columns were loaded with approximately 250 bed volumes (BVs) of feed solution at 45 C and at 1.5 to 12 BV per hour (0.15 to 1.2 cm/min). The columns were then eluted with 29+ BVs of HNO3 processed at 25 C and at 1.4 BV/h. The two independent tracers allowed analysis of the on-column cesium interaction between the loading and elution solutions. The objective of these tests was to improve the correlation between the spent resin cesium content and cesium leached out of the resin in subsequent loading cycles (cesium leakage) to help establish acid strength and purity requirements.

Download or read book Development of an Approach to Modeling Loading and Elution of Spherical Resorcinol Formaldehyde Ion Exchange Resin written by and published by . This book was released on 2011 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: 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 NO3). 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 HNO3 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 (SO3H−) groups; carboxylic (COOH−) groups, and resorcylic (OH−) 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.

Download or read book Fire Safety Tests for Cesium loaded Spherical Resorcinol Formaldehyde Resin written by and published by . This book was released on 2012 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book An Engineering Evaluation of Spherical Resorcinol Formaldehyde Resin written by and published by . This book was released on 2010 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: 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 for 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).

Download or read book Ion Exchange Modeling for Removal of Cesium from Hanford Waste Using Resorcinol Formaldehyde Resin written by and published by . This book was released on 2004 with total page 5 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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. 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.

Download or read book Spherical Resorcinol Formaldehyde Synthesis by Inverse Suspension Polymerization written by and published by . This book was released on 2005 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Base catalyzed sol-gel polycondensation of resorcinol (1,3-dihydroxybenzene) with formaldehyde by inverse suspension polymerization leads to the formation of uniform, highly cross-linked, translucent, spherical gels, which have increased selectivity and capacity for cesium ion removal from high alkaline solutions. Because of its high selectivity for cesium ion, resorcinol-formaldehyde (R-F) resins are being considered for process scale column radioactive cesium removal by ion-exchange at the Waste Treatment and Immobilization Plant (WTP), which is now under construction at the Hanford site. Other specialty resins such as Superlig{reg_sign} 644 have been ground and sieved and column tested for process scale radioactive cesium removal but show high pressure drops across the resin bed during transition from column regeneration to loading and elution. Furthermore, van Deemter considerations indicate better displacement column chromatography by the use of spherical particle beads rather than irregularly shaped ground or granular particles. In our studies batch contact equilibrium experiments using a high alkaline simulant show a definite increase in cesium loading onto spherical R-F resin. Distribution coefficient (Kd) values ranged from 777 to 429 mL/g in the presence of 0.1M and 0.7M potassium ions, respectively. Though other techniques for making R-F resins have been employed, to our knowledge no one has made spherical R-F resins by inverse suspension polymerization. Moreover, in this study we discuss the data comparisons to known algebraic isotherms used to evaluate ion-exchange resins for WTP plant scale cesium removal operations.

Download or read book Ion Exchange Modeling Of Cesium Removal From Hanford Waste Using Spherical Resorcinol Formaldehyde Resin written by and published by . This book was released on 2007 with total page 222 pages. Available in PDF, EPUB and Kindle. Book excerpt: This report discusses the expected performance of spherical Resorcinol-Formaldehyde (RF) ion exchange resin for the removal of cesium from alkaline Hanford radioactive waste. Predictions of full scale column performance in a carousel mode are made for the Hot Commissioning, Envelope B, and Subsequent Operations waste compositions under nominal operating conditions and for perturbations from the nominal. Only the loading phase of the process cycle is addressed in this report. Pertinent bench-scale column tests, kinetic experiments, and batch equilibrium experiments are used to estimate model parameters and to benchmark the ion-exchange model. The methodology and application presented in this report reflect the expected behavior of spherical RF resin manufactured at the intermediate-scale (i.e., approximately 100 gallon batch size; batch 5E-370/641). It is generally believed that scale-up to production-scale in resin manufacturing will result in similarly behaving resin batches whose chemical selectivity is unaffected while total capacity per gram of resin may vary some. As such, the full-scale facility predictions provided within this report should provide reasonable estimates of production-scale column performance.

Download or read book Cesium Isotherm Testing with Spherical Resorcinol Formaldehyde Resin at High Sodium Concentrations written by and published by . This book was released on 2016 with total page 96 pages. Available in PDF, EPUB and Kindle. Book excerpt: Washington River Protection Solutions (WRPS) is developing a Low-Activity Waste Pretreatment System (LAWPS) to provide low-activity waste (LAW) directly to the Hanford Tank Waste Treatment and Immobilization Plant (WTP) Low-Activity Waste Facility for immobilization. The pretreatment that will be conducted on tank waste supernate at the LAWPS facility entails filtration to remove entrained solids and cesium (Cs) ion exchange to remove Cs from the product sent to the WTP. Currently, spherical resorcinol-formaldehyde (sRF) resin (Microbeads AS, Skedsmokorset, Norway) is the Cs ion exchange resin of choice. Most work on Cs ion exchange efficacy in Hanford tank waste has been conducted at nominally 5 M sodium (Na). WRPS is examining the possibility of processing supernatant at high Na concentrations--up to 8 M Na--to maximize processing efficiency through the LAWPS. Minimal Cs ion exchange work has been conducted at 6 M and 8 M Na concentrations.

Download or read book MODELING RESULTS FROM CESIUM ION EXCHANGE PROCESSING WITH SPHERICAL RESINS written by and published by . This book was released on 2011 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Ion exchange modeling was conducted at the Savannah River National Laboratory to compare the performance of two organic resins in support of Small Column Ion Exchange (SCIX). In-tank ion exchange (IX) columns are being considered for cesium removal at Hanford and the Savannah River Site (SRS). The spherical forms of resorcinol formaldehyde ion exchange resin (sRF) as well as a hypothetical spherical SuperLig{reg_sign} 644 (SL644) are evaluated for decontamination of dissolved saltcake wastes (supernates). Both SuperLig{reg_sign} and resorcinol formaldehyde resin beds can exhibit hydraulic problems in their granular (nonspherical) forms. SRS waste is generally lower in potassium and organic components than Hanford waste. Using VERSE-LC Version 7.8 along with the cesium Freundlich/Langmuir isotherms to simulate the waste decontamination in ion exchange columns, spherical SL644 was found to reduce column cycling by 50% for high-potassium supernates, but sRF performed equally well for the lowest-potassium feeds. Reduced cycling results in reduction of nitric acid (resin elution) and sodium addition (resin regeneration), therefore, significantly reducing life-cycle operational costs. These findings motivate the development of a spherical form of SL644. This work demonstrates the versatility of the ion exchange modeling to study the effects of resin characteristics on processing cycles, rates, and cold chemical consumption. The value of a resin with increased selectivity for cesium over potassium can be assessed for further development.

Download or read book Modeling Ion Exchange Processing With Spherical Resins For Cesium Removal written by and published by . This book was released on 2012 with total page 32 pages. Available in PDF, EPUB and Kindle. Book excerpt: The spherical Resorcinol-Formaldehyde and hypothetical spherical SuperLig(r) 644 ion-exchange resins are evaluated for cesium removal from radioactive waste solutions. Modeling results show that spherical SuperLig(r) 644 reduces column cycling by 50% for high-potassium solutions. Spherical Resorcinol Formaldehyde performs equally well for the lowest-potassium wastes. Less cycling reduces nitric acid usage during resin elution and sodium addition during resin regeneration, therefore, significantly decreasing life-cycle operational costs. A model assessment of the mechanism behind ''cesium bleed'' is also conducted. When a resin bed is eluted, a relatively small amount of cesium remains within resin particles. Cesium can bleed into otherwise decontaminated product in the next loading cycle. The bleed mechanism is shown to be fully isotherm-controlled vs. mass transfer controlled. Knowledge of residual post-elution cesium level and resin isotherm can be utilized to predict rate of cesium bleed in a mostly non-loaded column. Overall, this work demonstrates the versatility of the ion-exchange modeling to study the effects of resin characteristics on processing cycles, rates, and cold chemical consumption. This evaluation justifies further development of a spherical form of the SL644 resin.

Download or read book Storage and Aging Effects on Spherical Resorcinol Formaldehyde Resin Ion Exchange Performance written by and published by . This book was released on 2007 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: 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 to 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.

Download or read book Real Waste Testing of Spherical Resorcinol Formaldehyde Ion Exchange Resin written by and published by . This book was released on 2009 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: 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 with 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.

Download or read book Alternate Methods for Eluting Cesium from Spherical Resorcinol Formaldehyde Resin written by and published by . This book was released on 2009 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: 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 (HNO3). The nitric acid eluate, containing the radioactive cesium, would be combined with the sludge from the waste tanks and would 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 HNO3 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.

Download or read book Fire Safety Tests for Spherical Resorcinol Formaldehyde Resin written by and published by . This book was released on 2012 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Evaluation of Potential Eluants for Non Acid Elution of Cesium from Spherical Resorcinol Formaldehyde Resin written by and published by . This book was released on 2011 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Ion Exchange column loading and elution of cesium from spherical resorcinol-formaldehyde resin have been conducted for two potential non-acid eluants -(NH4)2CO3 and CH3COONH4. The results revealed encouraging cesium elution performance. 100% elution was achieved in at most 22 hours (≈28 bed volumes) of elution. Elution performance was fairly high at 6 hours (≈8 bed volumes) of elution for some of the eluants and also practically comparable to the benchmark acid eluant (HNO3). Hence, it is quite possible 100% percent elution will be closer to the 6th hour than the 22nd hour. Elution is generally enhanced by increasing the concentration and pH of the eluants, and combining the eluants.

Download or read book Spherical Resorcinol Formaldehyde Resin for the Removal of Cesium from Hanford Tank Waste written by WILLIAM. WILMARTH and published by . This book was released on 2006 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: