Adamson, D. J.

Duffey, C. E.

Fondeur, F. F.

Fowley, M. D.

King, W. D.

Steeper, T. J.

Steimke, J. L.

Williams, M.

Wilmarth, William R.

UNT Digital Library

Spherical Resorcinol-Formaldehyde Resin for the Removal of Cesium from Hanford Tank Waste W. R. Wilmarth, W. D. King, F. F. Fondeur, D. J. Adamson, M. D. Fowley, J. L. Steimke, T. J. Steeper, M. Williams, and C. E. DuffeyWSRC-MS-2006-00257May 200630th Actinide Separations Conference 2Pretreatment ProcessUltra-filtrationSr/Actinide RemovalCesium Ion ExchangeSolidsPretreatedHigh Level WasteEluatePretreatedLAWPermeateWaste Receipt & Adjustment30th Actinide Separations Conference 3Treated LAWIon Exchange ColumnsCesium Ion Exchange SystemDilute causticDI waterNitric acidDI waterDilute caustic• Loading time needs to exceed restoration time• Less than 10 psi pressure drop per resin bed at flow rate of 22 gpm• Decontamination needs to exceed  1000 to 4000 for effluent of lag column• Many cycles or gallons processed before resin disposal is desiredUp flow waste introductionFeedVessel30th Actinide Separations Conference 4Baseline IX Resin - SuperLig® 644SL644 • WTP contract specified resin• Meets contract cesium removal and throughput needs• Qualified for use in WTP• Processes 900 to 1500 gallon waste per gallon resin (Envelope A, up to 10 cycles)• Sole source, proprietary product• Ground gel non-spherical form: Fractures, softens and adheres in multiple cycles limiting number of cycles of use due to pressure drop or channeling30th Actinide Separations Conference 5Development of RF as an Alternative• Support resin production for commissioning• Resolve any post-commissioning operating information needs(TBD)Testing – Stage 3• Developed alternative IX R&T Plan as part of Implementation Plan – no equipment changes (Aug to Oct 2002)Implementation Plan• Conducted engineering study• Selected RF as best potential alternative for Cs removal (Apr to Jun 2002)Engineering Study• Established need to have backup or alternative to SL-644 (Jan to Mar 2002)Identified Need• Scale-up production• Qualify for commissioningIn-Progress (2004 to 2006)Testing – Stage 2Testing – Stage 1• Tested 12 RF batches  from four vendors• Concluded RF most likely will meet requirements• Recommended specific spherical macroporous  RF for subsequent testing and scale-up (2003)30th Actinide Separations Conference 6SL644GGRFGGRFRF grown inside 0.8% polystyreneTested Resins30th Actinide Separations Conference 7SRNL Phase II Objectives Determine physiochemical stability of Spherical RF as a functionof chemical thermal and radiolytic exposure Determine gas generation rates under– Normal operation to assist purge ventilation design – Abnormal operation to size column relief devices Measure extent of nitration of resin during exposures to nitric acid Perform pilot-scale testing to assess resin viability Measure resin performance as a function of waste composition, regulatory compliance and develop modeling capability30th Actinide Separations Conference 8Status of Resin Stability Spherical RF and SuperLig ® 644 exhibit reaction with nitric acid with 2 reactions– Nitration and Oxidation– Energy of nitrated resin product is very low Thermal and radiolytic stability of Spherical RF exceeds baseline resin dramatically Not without any drawbacks– Higher gas generation during extreme acid contact– Same H2 generation under normal radiation dose rates but less total gas30th Actinide Separations Conference 9Modeling Nitration Reaction Heat and gas generation rate in the column is determined by the rate of reaction between the resin and nitric acid.  To determine the intrinsic rate of reaction between nitric and RF resin a series of tests were conducted looking at – different nitric acid molarity (to determine reaction rate dependence on nitric acid)– different temperatures at a given molarity (in this case 3M) to determine the activation energy of the reaction. Testing was conducted using a Differential Scanning Calorimeter and an Accelerated Rate Calorimeter.  The DSC data was used to generate the model.  The ARC data was used against the model predictions for scale up process 30th Actinide Separations Conference 1000.10.20.30.40.50.60.70.80.911 10 100 1000Time (minutes)Conversion1.5 M2.0 M2.5 M3.0 M3.5 M• The resin reaction with Nitric acid at different nitric acid molarity clearly shows a “S” shaped curve indicative of autocatalytic behavior. • In addition the onset of the reaction occurred faster the higher the nitric acid concentration (again indicative of a slow initiating reaction that depends on [HNO3]Effect of Nitric Acid Molarity: Functional Form of the Reaction30th Actinide Separations Conference 11Modeling: Results Based on the molarity tests, the deduced reaction is as follows:¾ Resin + HNO3Æ Resin-NO2 + Intermediates¾ Resin + Intermediates Æ 2 Intermediates¾ Resin-NO2 + HNO3Æ gas The rate of the reaction is then given as follows:¾ − Rate = k1 (resin)n (HNO3)m + k2(HNO3) Determined the concentration of resin from the partial areas of the DSC curve.30th Actinide Separations Conference 12-0.10.10.20.40.6Heat flow-0.2 0 .2 .4 .6 .8 1 1.2ConversionHeat flowHeat flow051015Heat Flow-0.2 0 .2 .4 .6 .8 1 1.2ConversionHeat FlowHeat Flow• Output from the DSC data fitted to the autocatalytic model to determine the exponent of the resin and nitric acid dependency.  • Best values for the nitric acid and resin exponent is 1.5 and 1 respectively as can be seen in the table.1.4613.51.41.431.61.222.51.20.9121.30.41.5Nitric Acid (m)Resin (n)Molarity1.5 Molar HNO33 Molar HNO3Dependency of the Nitric Acid and Resin on the Reaction Rate30th Actinide Separations Conference 13Ln (Rate Constant) = -23514 (1/T) + 86.347R2 = 0.8690123456780.0034 0.00345 0.0035 0.00355 0.0036 0.003651/T (1/Kelvin)Log (Rate Constant ) .Activation Energy = 0.2 E6 Joules/moles• Determine the overall rate constant for the nitration reaction from the experiments where the reaction was conducted at different temperatures.   Rate (mol/m3sec) = 2.25 E 16 Exp (-198,133/RT) (HNO3){1+(HNO3)0.5}Model: Rate Constant Determination30th Actinide Separations Conference 149.703.241.252.8474.458.513.41Cycle 1419.503.671.242.8574.3104.226.95Cycle 139.713.621.242.8574.152.513.42Cycle 121.303.221.242.8573.97.91.80Cycle 1142.733.161.242.8673.5263.559.05Cycle 1019.503.321.252.9673.4118.026.95Cycle 99.713.221.252.8173.958.013.42Cycle 89.703.401.252.9873.758.013.41Cycle 79.692.671.253.0073.5 (unlevel)74.013.39*  Cycle 69.693.641.263.0573.255.013.39Cycle 59.713.431.253.0173.558.013.42Cycle 419.503.231.263.0472.3123.026.95Cycle 39.703.221.263.0073.061.013.41Cycle 21.313.391.263.0572.57.91.81Cycle 19.72.981.263.0071.264.413.41Cycle 029.693.291.263.1073.0 (unlevel)61.813.39*  Cycle 01Simulantflow, gpmPermeability10^6 * cm^2Simulantdensityg/mLSimulantViscositycpresin ht.in simulantcmSimulantDP,Inches H2OSimulantVelocitycm/minCycle* Simulant Introduction Downflow24” IX Column Hydraulic Summary 30th Actinide Separations Conference 15Cycle 10, dP Across RF BedResin Bed Pressure Drop DPIX8   24" RF Cycle 10-500501001502002503000 2 4 6 8 10 12 14 16time, hoursDP, inches waterDPIX8simulantdownflowupflow ofregenerant0.1 MNaOHacidwaterwaterupflowsimulant9.7 psi at over 3x maximum flow rate for plant operation30th Actinide Separations Conference 16RF Resin Bed Permeability in AP-101 Simulant in 24" Column0.00.51.01.52.02.53.03.54.01 3 5 7 9 11 13 15Cummulative Cycle #Permeability in 1E-10 m^29.7 gpm after upflow introduction 19.3 gpm after upflow introduction43 gpm after upflow introduction 1.3 gpm after upflow introduction9.7 gpm after downflow introduction WTP design basis - 9.7 psi @ 22 gpm, 600 gal bed, 53" ID, 5 cpPermeability = (Bed Height x Velocity x Viscosity) / Pressure DropPermeability far exceeds requirements and is not affected by multiple cycles.Pilot Column Performed30th Actinide Separations Conference 17Permeability vs. Frictional ForcesPermeability in AP-101 vs. Flow Drag + Bed Negative Buoyancy 0.00.51.01.52.02.53.03.54.00 50 100 150 200 250 300flow drag + bed negative buoyancy in inches waterPermeability in 1E-10 m^224" w ith upflow  sim. Intro.WTP design basis - 9.7 psi @ 22 gpm, 5 cp, 600 gal, 53 inch ID30th Actinide Separations Conference 18Change in Bed Height with CyclesResin Bed Height in Simulant01020304050607080-2 0 2 4 6 8 10 12 14cycleCycles 01 and  6 (Downflow) had a 10 cmtilt across it so no accuratebed height could be determined Bed Height, cm30th Actinide Separations Conference 19RF Resin Micrographs Before and After CyclingNew Virgin RF-641, H form RF-641 after 16 Cycles, H form30th Actinide Separations Conference 20Micrograph of FinesRF-641 brownish colored fines after 16 cycles30th Actinide Separations Conference 21Color Change over Test CampaignCycle 14 Upflow RegenerationCycle 01 Upflow Regeneration Note the dark colored  particles throughout the resin bed after 16 total cycles 30th Actinide Separations Conference 22Resin in Spent/Recycle Streams 24” IX ColumnOnly the Collection Tank 1 Rinse Water Sock had resin fines of interest 30th Actinide Separations Conference 23Pilot-scale RF Testing Overview  A total of 16 cycles were completed in the 24” IX System The RF resin performed very well throughout the campaign No pressure drop increase across the bed with cycles– 9.7 gpm simulant flow,  approximately dP 60" w.c. – 19.5 gpm simulant flow, approximately  dP 120" w.c.– 43 gpm simulant flow, dP 264" w.c. Radial dP indicates no channeling occurring in RF bed Bed permeability essential remained constant– 3.3 x 10 -6 cm2 average and well above design limits No fissures or channeling observed  RF resin "bleeds" none to very little Before and after testing PSD of RF indicate excellent results Micrographs indicate some resin particle breakage/damage 30th Actinide Separations Conference 24Pilot-scale RF Testing Overview Cont. Upflow Regeneration performed best– 9.0 gpm for 30 minutes then reduce flow to – 1.42 gpm for 20 minutes Upflow Simulant Introduction performed best– 1.81 gpm for 52 minutes and increase flow to – 2.89 gpm to finish CV Downflow Introduction of simulant created undesirable bed– Cycle 01 and Cycle 6  Bed floated higher than expect during Upflow Simulant Introduction on Cycle 12 and Cycle 14 Cs removal of RF resin excellent after 13 cycles, 24” IX– Cs in the effluent never exceeded the detection limit, 1µg/L30th Actinide Separations Conference 25Summary Spherical RF continues to out perform baseline technology (SuperLig® 644)– Increased radiation stability from Cs Capacity perspective– Hydraulic performance is outstanding– Flammable gas generation same as baseline technology Actual waste testing at PNNL going well Isotherm modeling continuing at SRNL Regulatory analysis of spent resin planned for early summer 2006

Spherical Resorcinol-Formaldehyde Resin for the Removal of Cesium from Hanford Tank Waste

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Spherical Resorcinol-Formaldehyde Resin for the Removal of Cesium from Hanford Tank Waste

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