ICEM’ 11– Reims France26 Septembre 2011

Presented by: Albert A. KrugerGlass Scientist

Supervisor, Vitrification Group of theDOE WTP Project Office Engineering Division

High Waste Loading Glass Formulations for Hanford High-Aluminum HLW Streams

wP - 59388

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July 2011

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Generation of Hanford Tank Wastes

9 Reactors; 4 Fuel Reprocessing Flowsheets; 100,000 MT Fuel Processed

In Fiscal Year 2007, ORP initiated a testing program to develop and characterize HLW & LAW glasses with higher waste loadings, and where possible higher throughput, to meet the processing and product quality requirements.

This effort spans the investigation of the melt dynamics and cold cap properties to vitrification processes at the conditions close to those that exist in continuous waste glass melters.

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Glass Formulation for HLW & LAW Treatment

Background:Current estimates indicate that the number of HLW canisters to

be produced in the WTP is 13,500 (equivalent to 40,500 MT glass). The ca. 50,000 MT of sodium to be processed into glass equates to 588,000 tons of ILAW glass.

The current glass formulation efforts have been conservative in terms of achievable waste loadings.

These formulations have been specified to ensure the glasses are homogenous, preclude secondary phases (sulfate-based salts or crystalline phases), are processable in joule-heated, ceramic-lined melters and meet WTP Contract terms.

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Glass Formulation for Waste Treatment

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WTP Flow Sheet - Key Process Flows

LAWVitrification

(90+% of waste mass)

HLWVitrification

(90+% ofwaste activity)

Pretreatment(solid/liquid

separation – Cs, Sr, TRU removal)

SLUDGE

SUPERNATANT

MaximizeMass

MaximizeActivity

Hanford TankWaste

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It is likely that the capacity of the HLW vitrification plant can be increased significantly by implementation of a variety of low-risk, high-probability changes, either separately or in combination. These changes include:

• Operating at the higher processing rates demonstrated at the HLW pilot melter

• Increasing the glass waste loading in HLW glasses for wastes that are challenged by Al, Al plus Na, Bi, and Cr.

• Operating the melter at a slightly higher temperature

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Melter Scale Comparison

WTP High Level Waste 3.75 m2

West Valley 2.2 m2

Savannah River DWPF-SRS

2.4 m2

WTP Low Activity Waste RPP-LAW 10 m2

EnergySolutions M-Area Mixed Waste

DM-5000 5m2

LAW Pilot DM-3300 3.3 m2

Hanford HLW Pilot

DM-1200 1.2 m2

EnergySolutions/VSL Test Melters DM-100 0.11 m2

EnergySolutions/VSL Test Melters DM-10 0.02 m2

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Oxide Compositions of Limiting Waste Streams (wt%)Waste

Component Bi Limited Cr Limited Al Limited Al and Na Limited

Al2O3 22.45% 25.53% 49.21% 43.30%B2O3 0.58% 0.53% 0.39% 0.74%CaO 1.61% 2.47% 2.21% 1.47%Fe2O3 13.40% 13.13% 12.11% 5.71%Li2O 0.31% 0.36% 0.35% 0.15%MgO 0.82% 0.16% 0.24% 0.44%Na2O 12.97% 20.09% 7.35% 25.79%SiO2 12.04% 10.56% 10.05% 6.22%TiO2 0.30% 0.01% 0.02% 0.35%ZnO 0.31% 0.25% 0.17% 0.36%ZrO2 0.40% 0.11% 0.81% 0.25%SO3 0.91% 1.52% 0.41% 0.44%Bi2O3 12.91% 7.29% 2.35% 2.35%ThO2 0.25% 0.04% 0.37% 0.04%Cr2O3 1.00% 3.07% 1.07% 1.44%K2O 0.89% 0.37% 0.29% 1.34%U3O8 3.48% 7.59% 7.25% 4.58%BaO 0.02% 0.03% 0.11% 0.06%CdO 0.00% 0.01% 0.05% 0.02%NiO 3.71% 1.06% 0.82% 0.20%PbO 0.48% 0.48% 0.84% 0.18%P2O5 9.60% 3.34% 2.16% 4.10%

F- 1.58% 2.00% 1.37% 0.46%Total 100.00% 100.00% 100.00% 100.00%

These approaches successfully demonstrated increases in glass production rates and significant increases in waste loading at the nominal melter operating temperature of 1150° C.

Results of this work have demonstrated the feasibility of increases in waste-loading from about 25 wt% to 33-55 wt% (based on oxide loading) in the glass, depending on the waste stream.

Results of this work have resulted in IHLW glasses with waste loadings at 50 wt% (with >25 wt% Al2O3); and

Glass throughput rates in excess of 3x commissioning targets.

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Glass Formulation for HLW Treatment

Reduction in HLW Canister Count70% 62% 48% 59%

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Bi Limited Cr Limited Al+Na Limited Al LimitedWaste Type

Was

te O

xide

Loa

ding

WTP Contract Minimum

Experimental

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Composition and Properties of Aluminum Limited Waste and GlassFormulation HWI-Al-19 with 45% Waste Loading (wt%)

- Al-Limited Waste*

Waste in Glass

Glass Forming Additives

Target GlassHWI-Al-19

Al2O3 53.27 23.97 - 23.97B2O3 0.42 0.19 19.00 19.19BaO 0.12 0.05 - 0.05Bi2O3 2.54 1.14 - 1.14CaO 2.39 1.08 4.50 5.58CdO 0.05 0.02 - 0.02Cr2O3 1.16 0.52   0.52

F 1.48 0.67 - 0.67Fe2O3 13.11 5.90 - 5.90K2O 0.31 0.14 - 0.14Li2O 0.38 0.17 3.40 3.57MgO 0.26 0.12 - 0.12Na2O 7.96 3.58 6.00 9.58NiO 0.89 0.40 - 0.40P2O5 2.34 1.05 - 1.05PbO 0.91 0.41 - 0.41SO3 0.44 0.20 - 0.20SiO2 10.88 4.90 22.10 27.00TiO2 0.02 0.01 - 0.01ZnO 0.18 0.08 - 0.08ZrO2 0.88 0.39 - 0.39Sum 100.0 45.0 55.0 100.0

* Renormalized after removal of radioactive components

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Composition and Properties of Aluminum Limited Waste and GlassFormulation HWI-Al-19 with 45% Waste Loading (wt%)

Cont’d

Viscosity @1150ºC, P 33

Conductivity @1150ºC, S/cm 0.27

Crystal Content, As Melted None

Crystal Content, 72 hr at 950oC 1.3

Crystal Content, CCC 1.9

TCLP Pass

PCT, g/L

- DWPF-EA HWI-Al-19 -

B 16.7 0.654 B

Li 9.6 0.794 Li

Na 13.3 0.624 Na

- DWPF-EA HWI-Al-19 -

- Empty data field

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Composition of LAW Waste Stream and Contributions to Melter Feed andProduct Glass

UFP-VSL-00062A Contract Run UF Permeate Tank: 9,400 Data Points for Liquids

Amount required to replace 6 wt% Na2O in 100 kg glass

Components Units Bulk Average Moles Grams

Oxides in Glass(wt%)

Na+ mol/kg water 4.43 193.5 4452 Na2O - 6.00

Al(OH)4 mol/kg water 0.27 11.9 322 Al2O3 - 0.61

Na+ mol/mol Al 16.23 - - -

-OH mol/mol Al 10.22 121.9 2072 -

NO3 mol/mol Al 2.91 34.7 2152 -

-NO2 mol/mol Al 0.76 9.1 417 -

-2PO4 mol/mol Al 0.18 2.1 204 P2O5 - 0.15

-2SO4 mol/mol Al 0.14 1.7 160 SO3 - 0.13

wt% water % 79.7 - 43690  

Total 53469 6.89

- Empty data field

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Compositions (wt%) and Properties of Aluminum-Limited Waste and GlassFormulation HWI-Al-19LW with 45% HLW Waste Loading

Oxides Al-Limited Waste*

HLW Oxidesin Glass

LAW Oxidesin Glass

Glass Forming Additivesin Glass

Target Glass HWI-Al-19LW

Al2O3 53.27% 23.97% 0.61% —# 24.58%B2O3 0.42% 0.19% — 19.00% 19.19%BaO 0.12% 0.05% — — 0.05%Bi2O3 2.54% 1.14% — — 1.14%CaO 2.39% 1.08% — 3.61% 4.69%CdO 0.05% 0.02% — — 0.02%Cr2O3 1.16% 0.52% — — 0.52%

F 1.48% 0.67% — — 0.67%Fe2O3 13.11% 5.90% — — 5.90%K2O 0.31% 0.14% — — 0.14%Li2O 0.38% 0.17% — 3.40% 3.57%MgO 0.26% 0.12% — — 0.12%Na2O 7.96% 3.58% 6.00% — 9.58%NiO 0.89% 0.40% — — 0.40%P2O5 2.34% 1.05% 0.15% — 1.20%PbO 0.91% 0.41% — — 0.41%SO3 0.44% 0.20% 0.13% — 0.33%SiO2 10.88% 4.90% — 22.10% 27.00%TiO2 0.02% 0.01% — — 0.01%ZnO 0.18% 0.08% — — 0.08%ZrO2 0.88% 0.39% — — 0.39%

TOTAL 100.0% 45.0% 6.89% 48.11% 100.0%• Renormalized from after removal of radioactive components. # — indicates empty data field.

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Compositions (wt%) and Properties of Aluminum-Limited Waste and Glass Formulation HWI-Al-19LW with 45% HLW Waste Loading

Cont’d

Viscosity @ 1150°C, P 34.51

Electrical Conductivity @ 1150°C, S/cm 0.245

Crystal Content, 70 hrs at 950°C 1.7% (Spinel)

Crystal Content, CCC 2.9% (Spinel)

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Composition of LAW Waste Stream and Contributions to Melter Feed andProduct Glass

UFP-VSL-00062A Contract Run UF Permeate Tank: 9,400 Data Points for Liquids

Amount required to replace 6 wt% Na2O in 100 kg glass

Components Units Bulk Average Moles Grams

Oxides in Glass(wt%)

Na+ mol/kg water 4.43 193.5 4452 Na2O - 6.00

Al(OH)4 mol/kg water 0.27 11.9 322 Al2O3 - 0.61

Na+ mol/mol Al 16.23 - - -

-OH mol/mol Al 10.22 121.9 2072 -

NO3 mol/mol Al 2.91 34.7 2152 -

-NO2 mol/mol Al 0.76 9.1 417 -

-2PO4 mol/mol Al 0.18 2.1 204 P2O5 - 0.15

-2SO4 mol/mol Al 0.14 1.7 160 SO3 - 0.13

wt% water % 79.7 - 43690  

Total 53469 6.89

- Empty data field

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Waste loading increased to 50 wt% (26.6 wt% Al2O3); AndGlass production rate further increased

Most recent tests have reached

3000 kg/m2/d

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WTP Baseline

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Backup Information

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How is the Vitrified Waste Dispositioned?

High-Level Waste Canisters• 2’ x 14.75’ (0.61 x 4.5 m)• 6,600 pounds of glass• 600 canisters to be produced/year• Temporarily stored at Hanford until

National Repository opened

Low-Activity Waste Containers

• 4’ x 7.5’ (1.22 x 2.286 m)• 13,000 pounds of glass• 1,300 containers to be

produced/year• Disposed on Hanford Site