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DEVELOPMENT OF FRONTEND PROCESSING TO ALLOW USE OF HIGH-DENSITY LEU FOIL TARGETS IN CURRENT Mo-99 PRODUCTION FACILITIES M. Alex Brown, James L. Jerden Jr., Artem V. Gelis, Dominque C. Stepinski, Stan Wiedmeyer, Amanda Youker, Andrew Hebden,

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SLIDE 1

DEVELOPMENT OF FRONTEND PROCESSING TO ALLOW USE OF HIGH-DENSITY LEU FOIL TARGETS IN CURRENT Mo-99 PRODUCTION FACILITIES

  • M. Alex Brown, James L. Jerden Jr., Artem V. Gelis, Dominque C. Stepinski, Stan

Wiedmeyer, Amanda Youker, Andrew Hebden, George F. Vandegrift Chemical Sciences & Engineering Division Argonne National Laboratory June 29, 2014 Mo-99 Topical, Washington, D.C

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SLIDE 2

URANIUM ENRICHMENT

Nuclear

> 90% U-235 < 20% U-235

UAlx- Target

U-Foil

Chemical

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SLIDE 3

ARGONNE HD-TARGET FRONTEND PROCESSES

3

ACID PROCESS

Mo-99

IRRADIATE

LEU BASE PROCESS

PURIFICATION

Mo-99

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SLIDE 4

ARGONNE HD-TARGET FRONTEND PROCESSES

4

ACID PROCESS ELECTROCHEMICAL PROCESS

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SLIDE 5

ARGONNE HD-TARGET FRONTEND PROCESSES

 Prototype that can be scaled up  20-g U/batch  Resistant to radiation, corrosion, and hot-cell compatible  Warm test (DU)  Hot test (irradiated LEU)  Full-scale design  250-g U/batch  Resistant to radiation, corrosion, and hot-cell compatible  Cold test (Ni)  Warm test (DU)  Hot test (irradiated LEU)

5

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SLIDE 6

LEU IRRADIATIONS AT ARGONNE

  • LEU foils: 6 – 15 grams
  • Mimic fission recoil barriers: Al

(electrochemical) / Ni (acid)

  • Thermal neutron flux:

~1011 n×cm-2×s-1

  • 10 minute irradiation
  • Over-night cooling
  • Calculations: 50-100 µCi 99Mo

6

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SLIDE 7

THE ACID PROCESS

 Uranium foil dissolved in nitric acid

U + 4HNO3  UO2(NO3)2 + 2H2O + 2NO

 Nickel fission-recoil barrier and all other components dissolve also  Product fed to titania column for Mo recovery/separation and conversion to alkaline solution  Alkaline Mo-product solution to current purification process

7

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SLIDE 8

THE ACID PROCESS - DISSOLUTION

 Tested with Ni alone, DU, and finally with 242 g DU + 6 g irradiated LEU.  All components dissolve in 500 mL of nitric acid  100% of Ni and U foil were dissolved in 2 hours

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SLIDE 9

THE ACID PROCESS – Mo RECOVERY

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 Mo recovered on a titania column  Fission products  Acid wash followed by hydroxide strip  ~85% of fission products passed through; >90% removed after first wash  Column step completed in < 1 hour  99.3% Mo loaded; 98.4% Mo stripped

99Mo 127Sb

140Ba, 141Ce, 133I, 147Nd, 151Pm, 105Rh, 103Ru, 153Sm, 91Sr, 132Te, 237U, 93Y, 95Zr

titania

HNO3 + Uranium + Mo + Fission Products

99Mo + 127Sb + NaOH

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SLIDE 10

THE ELECTROCHEMICAL PROCESS

Dissolve Al in NaOH Dissolve U-foil in NaHCO3 Precipitate U + FP with CaO Alkaline Mo-product solution to current purification process

Irradiated LEU target

CCD - PEG TRUEX CCD - PEG TRUEX CCD - PEG TRUEX

Al(OH)4 U, Np, Pu, FP’s

Aluminum Precipitation TALSPEAK TALSPEAK TALSPEAK

99Mo sorption

CCD - PEG CCD - PEG CCD - PEG Uranium

NaOH NaHCO3 CaO

Decladding

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SLIDE 11

THE ELECTROCHEMICAL DISSOLVER

Anode / Cathode connections to a Magna-Power supply. SS basket with external heating ~2L of solution

BEFORE AFTER

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SLIDE 12

THE ELECTROCHEMICAL PROCESS

Al dissolved in ~30 minutes Operated at 9 V and 40 Amps Gases swept with N2 15 grams of LEU dissolved in 3.5 hours (98%) 600 mL of carbonate solution after dissolution

12

Mixing Vessel Anode Basket Thermo- couple Collection Tanks Dissolver Stir Motors In-line Filter N2 Feed

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SLIDE 13

PRECIPITATION & PRODUCT

99mTc 99Mo 135Xe 131I 133I 132I 135Xe 99Mo 99Mo

Clear color pH 13.0 Tc-99m, Mo-99, I-131 Trace amounts of 237U Fission Products Uranium precipitated with ~100 grams CaO Water rinse 10 µm in-line filter Strong signals from uranium and Fission Products

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SLIDE 14

Mo-99 RECOVERY IODINE RECOVERY

CCD

  • PEG

TRUEX CCD

  • PEG

TRUEX CCD

  • PEG

TRUEX

Al Digest Precipitation

TALSPEAK TALSPEAK TALSPEAK

Product

CCD

  • PEG

CCD

  • PEG

CCD

  • PEG

U Digest

No Mo-99 ~28 µCi Mo-99 2 µCi Mo-99

92%

Mo-99 Recovered 26 µCi Mo-99 Trace I-133 ~32 µCi I-133 ~1.6 µCi I-131

11 µCi I-133 0.9 µCi I-131

30-60% Iodine Recovered

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SLIDE 15

CONCLUSIONS

  • Two frontend processes were developed and tested at

Argonne to treat irradiated LEU foil for Mo-99 production.

  • An acid process used nitric acid to dissolve LEU

followed by Mo-99 recovery/separation on a titania column.

  • An electrochemical process utilized anodic dissolution
  • f LEU in carbonate followed by calcium precipitation.
  • Both processes demonstrated > 90% Mo-99 recovery.
  • Both processes can be fed into known Mo-purification

procedures.

15

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SLIDE 16

ACKNOWLEDGMENT

  • Bill Brown (Argonne)
  • ANL Central Shops
  • James Grudzinksi (Argonne)
  • Steve Sherman (ORNL)
  • CSE Division (ANL)
  • NNSA / GTRI

16

Thank you. Questions?

  • Vakhtang Makarashvili (Argonne)
  • Roman Gromov (Argonne)
  • Sergei Chemerisov (Argonne)
  • Lohman Hafenrichter (Argonne)
  • Jim Byrnes (Argonne)
  • Dave Rotsch (Argonne)

Work supported by the U.S. Department of Energy, National Nuclear Security Administration's (NNSA's) Office of Defense Nuclear Nonproliferation, under Contract DE-AC02-06CH11357. Argonne National Laboratory is operated for the U.S. Department

  • f Energy by UChicago Argonne, LLC.
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SLIDE 17

17

The submitted manuscript 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.

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SLIDE 18

EXTRA SLIDES

18

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SLIDE 19

ACID

  • Dissolution
  • Iodine
  • NOx gas
  • UREX
  • Purification

BASE

  • Dissolution
  • Iodine
  • NOx gas
  • UREX
  • Purification

19

ARGONNE HD-TARGET PROCESSES

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SLIDE 20

URANIUM TARGETS

U Metal

  • rthorhombic

ρ = 19.1 g/cm3 U-U = 2.8Å UO2 fluorite ρ = 10.9 g/cm3 U-O = 2.3Å

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SLIDE 21

URANIUM DISSOLUTION

  • Al dissolved in ~30 minutes
  • Operated at 9 V and 40 mAmps
  • Gases swept with N2
  • 15 grams of LEU dissolved in 3.5

hours (98%)

  • 600 mL of carbonate solution

after dissolution

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SLIDE 22

DISSOLVED URANIUM SOLUTION

  • Light-green color U(VI)
  • pH 10.0

133I 97Nb 97Zr 99mTc 237U

0.5 1 400 500 600 700 800 900

Absorbance

nm

No U(IV)

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SLIDE 23

PRECIPITATION AND FILTRATION

  • Uranium precipitated with ~100 grams CaO
  • Mixing vessel rinsed with water
  • Slurry fed through 10 µm in-line filter
  • ~1.2 L product solution
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SLIDE 24

Mo PURIFICATION

  • Product solution contacted with AG-MP-1 anion

exchange resin

  • Iodine and Molybdenum retained
  • Kd (Mo) = ~150 mL/g
  • α-Benzoin oxime precipitated Mo-carrier after

acidification

http://www.sigmaaldrich.com/catalog/product/aldrich/b8 908?lang=en&region=US

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SLIDE 25

FUTURE

  • More low-burnup and DU tests at ANL
  • Improve hot-cell compatibility
  • High-burnup tests
  • More XRD studies on Na-Ca-UO2-CO3

precipitate

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SLIDE 26

waste

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SLIDE 27

27

Low Temperature Low Pressure Alkaline Dissolution Process Scheme

Irradiated LEU foil target

CCD

  • PEG

TRUEX CCD

  • PEG

TRUEX CCD

  • PEG

TRUEX

NaOH/ NaAl(OH)4 CaCO3, Ca(OH)2, An, FP’s

Dissolution of Al barrier U precipitation TALSPEAK TALSPEAK TALSPEAK

99Mo sorption

CCD

  • PEG

CCD

  • PEG

CCD

  • PEG

U electrolysis

NaOH 1 M NaHCO3 CaO solid filtrate

Mechanical Decladding

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SLIDE 28

28

Target Dissolution

Nickel Foil 1 M NaHCO3 Ni/SS clips Uranium Foil Stirrer Ni Mesh Basket

_ +

Two-step process

  • 1. Dissolution of Al fission recoil barrier using NaOH
  • 2. Anodic dissolution (1 M NaHCO3 in a beaker with

intense stirring)

  • 8.8g DU foil dissolved in 45 minutes (0.0042

g/min·cm2)

  • 22g foil dissolved in 90 minutes

2.0 1.5 1.0 0.5 0.0

  • 0.5
  • 1.0
  • 20
  • 15
  • 10
  • 5

5 10 15 20

U foil

H2 O2

Current, A

E vs Hg/HgO/0.1 M NaOH, V U(VI)

Ni basket

cathodic anodic

U0 → UO2 → UO2+x → UO2(CO3)n

2-2n

fast surface reactions rate-limiting step

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SLIDE 29

29

Uranium Precipitation

Filtrate Solution

  • <1 mM CO3

2-

  • Trace U
  • Saturated Ca(OH)2
  • Would also contain soluble FPs
  • pH 12.7
  • No MoO4

2- is co-precipitated !

  • Kd (99Mo) ~ 340 mL/g on AG-MP1

XRD of Precipitate

  • CaCO3
  • A mixed Na-Ca-(UO2

2+ )-(CO3) phase

  • Would also contain insoluble FPs, Pu,

Np

  • SEM and TEM analysis will follow
  • Addition of CaO excess is

followed by a filtration step

  • The precipitate is very

easy to filter using a paper filter under gravity Precipitate

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SLIDE 30

30

New Dissolver Design

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SLIDE 31

Tc-99m

http://backreaction.blogspot.com/2 008/11/technetium-99.html

  • The most important medical

isotope in the world

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SLIDE 32

Mo-99/Tc-99m PRODUCTION

  • Canada produces half
  • 2016 deadline
  • A domestic supply is

needed

http://www.cins.ca/scat.html

  • Fission of highly-enriched U-235 can make

profitable amounts of Mo-99

Aecl.ca

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SLIDE 33

Mo-99 PRODUCTION STEPS

Well known for acid, what about base? Works with acid and base.

DIGEST URANIUM CHEMICAL SEPARATIONS PURIFY Mo-99

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SLIDE 34

ACID PROCESS

Mo-99

IRRADIATE

LEU BASE PROCESS

PURIFICATION

Mo-99

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SLIDE 35

SELECTED FISSION PRODUCT H2O CHEMISTRY

Mo Zr

La I

ACID BASE

Zirconium Zr4+, ZrO2 Zr(OH)x

4-x Polymer

Molybdenum MoO2

2+

MoO4

2-

Lanthanum La3+ La(OH)x

3-x

Iodine I2 I-, I3

  • , IO3
  • MASS

100 130

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SLIDE 36

IODINE

  • W. Gottardi, Iodine and Iodine Compounds in Disinfection, Sterilization, and Preservation,

S.S. Block, Lea &Febiger, Philadelphia, PA, USA, (2000).

Alkali promotes anionic iodine which stays in solution!

7 14

pH

  • I3
  • + I-
  • 131I2

Log M

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SLIDE 37

PROCESS DESIGN

  • Advantages of an alkali process:

– Less I2 – Iodine control could mean profit – No NOx

gas

– Relatively new concept – Mo purification fits well

  • Disadvantages:

– Uranium metal not readily digested in base – Precipitates – May be difficult to feed into UREX cleanup

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SLIDE 38

URANIUM CARBONATE

  • UO2

2+ and carbonate

– UO2(CO3)x

(2x-2)-

  • Precipitated with CaO

– Na-Ca-(UO2

2+ )-(CO3)x

phase

  • Most fission products co-

precipitate

  • Mo does not precipitate!

2 4 6 8 10 pH 20 40 60 80 100 % formation relative to UO2 UO2 (UO2)(CO3) (UO2)(CO3)2 (UO2)(CO3)3

Speciation diagram for uranium carbonate complexes. J.J. Katz et al. The Chemistry of the Actinide Elements, 2nd ed., diagram generated by M.A. Brown using HySS

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SLIDE 39
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SLIDE 40

product

99mTc 99Mo 135Xe 131I 133I 132I 135Xe 99Mo 99Mo

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SLIDE 41

Less U-235 enrichment New neutron flux New target design New target dissolution New uranium treatment

(Same purification steps)

Can we match the original Mo-99 yields using LEU?

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SLIDE 42

PILOT SCALE

  • Test with depleted uranium at

ANL

  • Test low-burnup at ANL LINAC
  • High-burnup
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SLIDE 43

WARM TEST

  • Demonstrated good electrical dissolution
  • 10 grams of depleted uranium dissolved in ~ 4 hours.
  • Precipitation step on a large scale.
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SLIDE 44

LOW-BURNUP TEST

  • ANL setup
  • LINAC neutrons
  • LEU foil

irradiated for 10 minutes

  • Cooled overnight
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SLIDE 45

DISSOLUTION IN ALKALI

  • Aluminum dissolves in NaOH
  • Uranium forms passive layer

Al Al(OH)4

  • solution!

U U(OH)3 UO2+x

X

fast surface reaction

http://www.gh.wits.ac.za/chemnotes/chem3028/Marques/InorgChem_Overview_2011_HMM.pdf

Need to manually pull electrons from U and UO2!

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SLIDE 46

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SLIDE 47

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