Chemical Processing Activities for 99 Mo production by ( ,n) and (n, ) reactions using enriched 100 Mo and 98 Mo targets Peter Tkac, David Rotsch, Alex Brown, Dominique Stepinski, Vakhtang Makarashvili, George Vandegrift Nuclear Engineering Division, Argonne National Laboratory Mo-99 Topical Meeting, August 31-Sepetember 3, 2015
ANL support to NorthStar Irradiation of sintered Mo targets using electron linac Chemical processing of irradiated targets Optimization of sintered Mo disks for density and dissolution kinetics Large scale dissolution process (300-600g of Mo per batch) Front-End purification of irradiated Mo Recycle process to recover valuable enriched 98 Mo and 100 Mo Radiation stability studies at VDG 2
Production of 99 Mo/ 99m Tc without U targets Reac actor tor product ction ion on Mo targe get Mo-100 Mo 100 Mo-92 Mo98 Mo-98 Mo 98 Mo99 Mo-94 9.67% 14.77% neutro ron Mo-95 9.23% 24.19% γ Mo-96 15.90% gamma Mo-97 9.56% 16.68% Mo-98 Ac Accelerat elerator or product ction ion Mo-100 γ Mo100 Mo99 gamma neutro ron Cyclotr tron on product ctio ion Enriched Mo-100 is available for ~$1000 per gram for kg quantities!!! Mo100 Tc99m Tc99m proto ton neutro ron 3
FY 15 production of 99 Mo at ANL 100 Mo 99 Mo in 6 disks, power Current Time, hrs. Energy (position) Ci 99% (1-6) 0.92 4kW 95µA 19 42 MeV 97.4% (3-8) 2.9 7.56kW 180µA 21 42MeV 95.1% (3-8) 2.2 7.56kW 180µA 19 42MeV 99% (3-8) 4.2 7.77kW 222µA 24.4 35MeV 1000 100 Mo-99, mCi MCNPX 100 Mo experimental enriched 10 Natural Mo 922 mCi ~300 mCi 1 0 5 10 15 20 25 30 disk position 4
Processing of irradiated disks 5
Optimizing sintered Mo disks production (ANL &ORNL) 1400 C Density = 89.7% Open Porosity = 7.1% Diss. Rate = 0.623 g/min 1500 C Density = 91.9% Open Porosity = 0.2% Diss. Rate = 0.361 g/min 1600 C Density = 94.0% Open Porosity = 0% Diss. Rate = 0.186 g/min SEM Images provided by Steve Nunn (ORNL) 6
Optimizing sintered Mo disks production (ANL &ORNL) 12 93.5 1.0 10 ~94% Mo disks sintered at 1200-1500 C) diss. rate, g/min open porosity, % ANL#80 150 ksi 0.8 8 ANL#80 200 ksi 6 Climax NPA 150 ksi 0.6 93.8 4 0.4 94.2 2 94.2 0.2 0 0 1 2 3 4 5 6 1100 1200 1300 1400 1500 1600 sintering temperature, C open porosity, % SEM Images of As-received Commercial NPA Powder and Reduced Small Batch (30 g) of ANL Recycled MoO 3 Powder. SEM images provided by Rick Lowden (ORNL). 7
Large scale dissolution processing New design 75g batch diss. 50% vs. 30% H 2 O 2 Total processing time 1h40min vs 4hrs 300g of Mo 300g of Mo frit Dissolution in H 2 O 2 >>> evaporation/ H 2 O 2 destruction >>> Fe co-precipitation of Zr&Nb >>> filtration >>> KOH added to make ~200g/L Mo in ~5M KOH 8
Large scale dissolution processing 9
Large scale dissolution processing 10
Large scale dissolution processing H 2 O 2 , diss. Mo, dissolution, evaporation, total, concentration # % vessel, L g hrs hrs hrs step 1 50 2 75 0.5 1.5 2 open to atm. 2 50 2 75 0.5 1.2 1.7 open to atm. 3 30 2 75 0.5 3.5 4 open to atm. 4 50 5 300 2 5.8 7.8 vacuum 5 50 5 300 2.7 6 8.7 vacuum 6 50 5 300 2 6.8 8.8 vacuum 7 30 5 300 1.4 6.4 7.8 vacuum 8 50 5 300 1.5 0.6 2.3 vacuum 9 50 5 300 1.3 0.7 2.2 vacuum 11
Removal of Zr and Nb Removal of Zr and Nb, % filtration 0.7% vol 4% vol 0.7% vol 4% vol 10mg/mL pH 0.22µm Fe(III) Fe(III) Fe(III)+Fe(II) Fe(III)+Fe(II) HZO 12 99.9 99.0 98.9 99.5 99.7 99.9 13 99.9 99.9 99.1 100 99.7 100 14 99.3 99.2 99.6 99.3 99.6 99.5 5M OH - 72.5 73 76.8 73.3 73.7 84.4 Removal of Zr and Nb with 1µl/mL 30% H 2 O 2 , % filtration 4% vol 4% vol 10% vol magnetite 10mg/mL pH 0.22µm Fe(III) Fe(III)+Fe(II) La(III) Fe 3 O 4 HZO 12 16.8 82.4 83.2 75.4 95.4 76.8 13 83.5 74.4 77.8 99.8 100 99.9 14 3 19.6 37.2 95.3 77.6 45.7 5M OH - 2 7.6 37.6 62.1 55.2 15.6 Fe=1M, La=10mg/mL 12
Large scale recovery of Mo by precipitation 1.5L of spent generator solution in 5M KOH containing ~300 g of Mo (MURR samples) 80% of K removed in AcA precipitation Mo precipitate washed with conc. HNO 3 (~7.5L of HNO 3 per wash, up to 9-10 washes are needed) ~75L of conc. HNO 3 used per batch Remove residual HNO 3 by heating Final Mo product as MoO 3 ready for reduction K 2 MoO 4 in 5M KOH Mo recovery: ~95%, product MoO 3 Mo Glacial AcA KAc waste K concentration in purified product <100mg-K/kg-Mo precipitation Published in J. Radioanal. Nucl Chem., 2015 DOI: 10.1007/s10967-015-4357-1 HNO 3 http://link.springer.com/article/10.1007/s10967-015-4357-1 HNO 3 recycle/ waste Mo precipitate wash Drying MoO 3 product 13
1000 99.6% Distribution ratio: 𝐸 𝑁𝑓 = [𝑁𝑓] 𝑝𝑠 100 98.3% D(Mo) trace [𝑁𝑓] 𝑏𝑟 97.2% 10 K distribution ratio 1 D K =1 × 10 -4 – 1 × 10 -5 50% TBP in 1-octanol 0.1 1 10 [HCl] Mo, M HCl, M Extr. % 0.35 7.1 97.6% 50% TBP in 1-octanol 0.36 6.9 97.5% 0.38 6.8 97.1% 0.40 6.6 97.4% 0.45 6.2 97.2% 14
50% TBP in 1-octanol 30% TBP in tetrachloroethylene 1 1 Mo load org exp Mo load org exp Mo load org calc Mo load org calc [Mo org], M [Mo org], M 0.1 0.1 0.01 0.01 0.001 1 10 100 1 10 100 {Cl-} {Cl-} Extraction constants determined for two Mo-TBP species: HMoO 2 Cl 3 2TBP MoO 2 Cl 2 (TBP HCl) 2 15
Feed Mo, K, and Minor Solvent Scrub Strip Impurities in HCL Diluted TBP HCl solution Aqueous NH 3 Scrub Strip Extraction Spent Raffinate Product Solvent HCl solution containing K (NH 4 ) 6 Mo 7 O 24 + NH 4 Cl For recycle to + Minor Impurities extraction section following conditioning with HCl Removal of NH 4 Cl 16
Mo S Strip Evaporati ation on Sublimati ation Differen rentia ial at ~340 C solubility so lity in ethano hanol-wa water ter NH 4 OH solution NH 4 OH solution mixtur ure Solid mixtur ure Solid mixtur ure NH NH 4 Cl Cl NH NH 4 Cl Cl NH 4 Cl NH Cl NH 4 Cl NH Cl (NH NH 4 ) 6 Mo Mo 7 O 24 24 (NH NH 4 ) 6 Mo Mo 7 O 24 24 (NH NH 4 ) 6 Mo Mo 7 O 24 24 (NH NH 4 ) 6 Mo Mo 7 O 24 24 Acetic acid ppt NH 4 OH waste NH 4 Cl solid waste NH 4 Cl solid waste Ethanol wash (NH (NH 4 ) 6 Mo Mo 7 O 24 24 MoO 3 product at MoO 3 product at 500 C 500 C 500 C MoO 3 product 17
Mo ppt after wash Mo ppt after heating at 500 C with AcA and EtOH ~500g of MoO 3 sent to ORNL for reduction to Mo metal and production of sintered Mo disks Mo ppt after Ammonium molybdate heating at 500 C (NH 4 ) 6 Mo 7 O 24 xH 2 O 18
Mo in ammonium 5M HCl strip MoO 3 KOH molybdate ppm (mg/kg-Mo) B ND ND 2.0 9.1 ND Na 9439 9712 24.7 10.9 9.3 Mg 29.6 21.7 4.8 4.0 5.1 Al 8.3 8.46 2.8 ND ND Si ND ND ND ND ND P ND ND 1838 ND ND Ti 26.7 64.1 37.3 13.7 12.4 Cr ND ND 5.2 ND ND Mn 1.9 0.55 0.4 ND ND Fe ND ND ND ND ND Co ND ND ND ND ND Ni ND ND 0.8 ND ND Cu 5255 7.7 23.3 ND 7.8 Zn 12.4 ND 24.6 2.4 3.1 Zr 0.6 0.37 0.1 ND ND Nb 2.8 1.53 1.5 2.9 2.7 Sn 86.2 19.2 22.3 24.0 20.5 Sb 4.7 4.1 4.2 ND ND Cs 0.8 0.66 0.7 0.2 0.1 W 237 259 138 164 159 K 1933673 1217949 454 257 233 K (%) 100% 63.0% 0.023% 0.013% 0.012% 19
Acknowledgement ANL – S. Chemerisov, R. Gromov, Ch. Jonah, T. Heltemes, M. Virgo, K. Wardle, C. Pereira, J. Copple, Y. Tsai, M. Kalensky, M. Bennett, A. Hebden, L. Hafenricher, K. Alford, K. Wesolowski, …… LANL – G. Dale, F. Romero, K. Woloshun, M. Holloway, D. Dalmas, … .. ORNL – R. Lowden, S. Nunn, Ch. Brian … .. NorthStar – J. Harvey … . Work supported by the U.S. Department of Energy, National Nuclear Security Administration's (MMM) Office , under Contract DE-AC02-06CH11357. The submitted presentation has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government. 20
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