[PPT] - enriched 100 Mo and 98 Mo targets Peter Tkac, David Rotsch, Alex PowerPoint Presentation

SLIDE 1

Chemical Processing Activities for 99Mo production by (,n) and (n,) reactions using enriched 100Mo and 98Mo 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

SLIDE 2

ANL support to NorthStar

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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 98Mo and 100Mo
Radiation stability studies at VDG

SLIDE 3

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Production of 99Mo/99mTc without U targets

14.77% 9.23% 15.90% 16.68% 9.56% 24.19% 9.67%

Mo-92 Mo-94 Mo-95 Mo-96 Mo-97 Mo-98 Mo-100

Mo Mo-100 100 Mo Mo-98 98

Enriched Mo-100 is available for ~$1000 per gram for kg quantities!!!

Mo100

γ

Mo99

gamma neutro ron

Ac Accelerat elerator

r product

ction ion

Mo100 Tc99m Tc99m

proto ton neutro ron

Cyclotr tron

n product

ctio ion

Mo98

γ

Mo99

neutro ron gamma

Reac actor tor product ction ion on Mo targe get

SLIDE 4

FY 15 production of 99Mo at ANL

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1 10 100 1000 5 10 15 20 25 30

Mo-99, mCi disk position

MCNPX experimental 100Mo

enriched 922 mCi Natural Mo ~300 mCi

100Mo

(position)

99Mo in 6 disks,

Ci power Current Time, hrs. Energy 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

SLIDE 5

Processing of irradiated disks

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SLIDE 6

Optimizing sintered Mo disks production (ANL &ORNL)

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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)

SLIDE 7

Optimizing sintered Mo disks production (ANL &ORNL)

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93.5 93.8 94.2 94.2

0.2 0.4 0.6 0.8 1.0 1 2 3 4 5 6

diss. rate, g/min
pen porosity, %

~94% Mo disks sintered at 1200-1500C)

2 4 6 8 10 12 1100 1200 1300 1400 1500 1600

pen porosity, %

sintering temperature, C

ANL#80 150 ksi ANL#80 200 ksi Climax NPA 150 ksi

SEM Images of As-received Commercial NPA Powder and Reduced Small Batch (30 g) of ANL Recycled MoO3 Powder. SEM images provided by Rick Lowden (ORNL).

SLIDE 8

Large scale dissolution processing

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frit 75g batch diss. 50% vs. 30% H2O2 Total processing time 1h40min vs 4hrs Dissolution in H2O2 >>> evaporation/ H2O2 destruction >>> Fe co-precipitation of Zr&Nb >>> filtration >>> KOH added to make ~200g/L Mo in ~5M KOH 300g of Mo 300g of Mo New design

SLIDE 9

Large scale dissolution processing

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SLIDE 10

Large scale dissolution processing

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Large scale dissolution processing

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# H2O2, % diss. vessel, L Mo, g dissolution, hrs evaporation, hrs total, hrs concentration step 1 50 2 75 0.5 1.5 2

pen to atm.

2 50 2 75 0.5 1.2 1.7

pen to atm.

3 30 2 75 0.5 3.5 4

pen 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

SLIDE 12

Removal of Zr and Nb

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Removal of Zr and Nb, % pH filtration 0.22µm 0.7% vol Fe(III) 4% vol Fe(III) 0.7% vol Fe(III)+Fe(II) 4% vol Fe(III)+Fe(II) 10mg/mL 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% H2O2, % pH filtration 0.22µm 4% vol Fe(III) 4% vol Fe(III)+Fe(II) 10% vol La(III) magnetite Fe3O4 10mg/mL HZO 12 82.4 83.2 75.4 95.4 16.8 76.8 13 74.4 77.8 99.8 100 83.5 99.9 14 19.6 37.2 95.3 77.6 3 45.7 5M OH- 7.6 37.6 62.1 55.2 2 15.6

Fe=1M, La=10mg/mL

SLIDE 13

Large scale recovery of Mo by precipitation

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Mo recovery: ~95%, product MoO3 K concentration in purified product <100mg-K/kg-Mo

Published in J. Radioanal. Nucl Chem., 2015 DOI: 10.1007/s10967-015-4357-1

http://link.springer.com/article/10.1007/s10967-015-4357-1

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. HNO3 (~7.5L of HNO3 per wash, up to 9-10 washes are

needed) ~75L of conc. HNO3 used per batch

Remove residual HNO3 by heating
Final Mo product as MoO3 ready for reduction

Mo precipitation

Glacial AcA K2MoO4 in 5M KOH HNO3 KAc waste HNO3 recycle/ waste

Mo precipitate wash Drying MoO3 product

SLIDE 14

Mo, M HCl, M

Extr. %

0.35 7.1 97.6% 0.36 6.9 97.5% 0.38 6.8 97.1% 0.40 6.6 97.4% 0.45 6.2 97.2%

0.1 1 10 100 1000 1 10

D(Mo) trace [HCl]

97.2% 99.6% 98.3%

50% TBP in 1-octanol Distribution ratio: 𝐸𝑁𝑓 = [𝑁𝑓]𝑝𝑠𝑕 [𝑁𝑓]𝑏𝑟 K distribution ratio DK=1×10-4 – 1×10-5 50% TBP in 1-octanol

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SLIDE 15

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50% TBP in 1-octanol 30% TBP in tetrachloroethylene Extraction constants determined for two Mo-TBP species: HMoO2Cl32TBP MoO2Cl2(TBPHCl)2

0.01 0.1 1 1 10 100

[Mo org], M {Cl-}

Mo load org exp Mo load org calc

0.001 0.01 0.1 1 1 10 100

[Mo org], M {Cl-}

Mo load org exp Mo load org calc

SLIDE 16

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Solvent

Diluted TBP

Feed Mo, K, and Minor Impurities in HCL Scrub

HCl solution

Strip

Aqueous NH3

Raffinate

HCl solution containing K + Minor Impurities

Product

(NH4)6Mo7O24+ NH4Cl

Extraction Strip Scrub

Spent Solvent

For recycle to extraction section following conditioning with HCl

Removal of NH4Cl

SLIDE 17

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Acetic acid ppt Ethanol wash MoO3 product at 500 C NH4OH solution Mo S Strip NH NH4Cl Cl (NH NH4)6Mo Mo7O24

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NH4OH waste NH4OH solution Evaporati ation

n

NH4Cl solid waste Sublimati ation at ~340C Solid mixtur ure NH NH4Cl Cl (NH NH4)6Mo Mo7O24

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NH4Cl solid waste Differen rentia ial so solubility lity in ethano hanol-wa water ter mixtur ure Solid mixtur ure NH NH4Cl Cl (NH NH4)6Mo Mo7O24

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NH NH4Cl Cl (NH NH4)6Mo Mo7O24

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MoO3 product at 500C

(NH (NH4)6Mo Mo7O24

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500C MoO3 product

SLIDE 18

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Mo ppt after wash with AcA and EtOH Mo ppt after heating at 500C Ammonium molybdate (NH4)6Mo7O24xH2O Mo ppt after heating at 500C ~500g of MoO3 sent to ORNL for reduction to Mo metal and production of sintered Mo disks

SLIDE 19

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Mo in KOH 5M HCl strip ammonium molybdate MoO3 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%

SLIDE 20

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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

f 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.