Processability of High Waste Loading Hanford LAW Feeds

Isabelle Muller - Vitreous State Laboratory - Catholic University of America

Processability of High Waste Loading Hanford LAW Feeds

Isabelle S. Muller

Vitreous State Laboratory

Washington,DC

1


Outline

1. LAW Glass formulations and melter tests (DM10 - DM100 -DM1200 - DM3300).

2. WTP Correlation design.

3. Enhanced waste loading ORP formulations.

4. Processing characteristics.

5. Strategies to improve processing. 1. Crucible evaluation

2. Melter evaluation

6. Proposed ORP Enhanced LAW Glass Correlation.

2


LAW:

waste

composition

3

70 75 80 85 90 95 100

AP-101 Sup

AZ-101 Sup

AZ-102 Sup

AN-102 Sup

AN-102 Sup

AN-104 DS

AN-104 Sup

AN-107 Sup

AN-105 Sup

AN-105 DS

SY-101 Sup

SY-101 Sup

AN-103 Sup

AN-103 DS

AW-101 Sup

AW-101 DS

AW-104 Sup

wt% oxide

Na2O

Al2O3

K2O

SO3

Cl

F

P2O5

Cr2O3

CaO

Fe2O3

≥75 wt% Na2O

• Al2O3

• K2O

• SO3

Glass

formulations are

either limited by

their content in

• Na2O, K2O

• SO3 (SO4/Na)


4

LAW Envelopes Contract (Mod.451)

Specification 7

Compositions requirements

Table TS-7.1 LAW Chemical Composition, Soluble Fraction Only

(maximum ratio, moles of analyte to moles of sodium)

Chemical Analyte Envelope

A

Envelope

B Envelope C

Al 0.25 0.25 0.25

Ca 0.04 0.04 0.04

Cl 0.037 0.089 0.037

Cr 0.0069 0.02 0.0069

F 0.091 0.200 0.091

Fe 0.01 0.01 0.01

K 0.18 0.18 0.18

NO2 0.38 0.38 0.38

NO3 0.80 0.80 0.80

PO4 0.038 0.13 0.038

SO4 0.01 0.07 0.02

TIC 0.30 0.30 0.30

TOC 0.50 0.50 0.50

U 0.0012 0.0012 0.0012

Na2O in Glass 14 wt% 3 wt% 10 wt%


5

Property Requirement(s)

Density < 3.7 g/ml

Liquidus Temperature < 950oC

LAW Canister Centerline Cooling Heat Treatment

Report amount of crystals

Glass Transition TG (onset) Report TG

PCT per ASTM C1285 Test conducted at glass to water

ratio of 1 gram of glass (-100 +200 mesh) per 10 ml of water at 90C

PCT-B, PCT-Na, PCT-Si

< 2.0 g/m2

VHT at 200oC for 24 days < 50 g/m2/day

Viscosity at 1100oC 10 to 150 P

Electrical Conductivity at 1100oC 0.1 to 0.7 S/cm

K-3 Refractory Corrosion WTP LAW glass formulation :neck corrosion of 0.035” on 6-day at 1208C High waste loading LAW ORP, a slightly higher neck corrosion value of 0.040” inches was used as a guide for acceptable corrosion characteristics


6

Early WTP LAW Formulations and Melter Testing

0

2

4

6

8

10

12

14

16

18

20

22

24

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09

Na 2

O (

wt%

in g

lass

)

SO4/Na molar ratio

A1

A2 (K2O >0.5 wt%)

A3 (High SO3)

C1

C2

B1 B2

Envelope A

Envelope C

Envelope B

• 3 scales of pilot melter

• ± 15% waste

• Transitions A2-B1, C2-A3, …

Production rate ~ 2000 Kg/m2/day

WTP LAW

10 m2

DM10

DM100

LAW Pilot

DM3300

0.021 m2

0.12 m2

3.3 m2

0.2

%

1.2

%

1/3

DM1200 1.2 m2

12

%


7

WTP LAW Correlation

Provides the procedure to calculate the mix

of glass-forming chemicals (GFCs)

required in the algorithm for batching the

low-activity waste (LAW) and (GFCs) in

the LAW melter feed preparation vessel.

It is designed to produce a glass composition

that will meet all contractual requirements.

The calculation is based on Al2O3,

Na2O, SO3, and K2O waste concentrations.


8

LAW Correlation

1. Based on maximum SO3/Na2O of Duramelter glasses

2. Alkali limited glasses for 0 < SO3 ≤ 0.35 wt%

Na2O + 0.66 K2O ≤ 21.5 wt%

3. Sulfate limited glasses for SO3 ≥ 0.35 wt%

Na2O (wt%) =

Na

SO45.42

99.30

06.801

875.35


9

0

5

10

15

20

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

Na

2O

wt%

SO3 wt%

Na2O (total)

Na2O (waste contribution)

Correlation

Glasses proposed for testing

Current Glasses caculated

LAWB45

A1:

A2:

C2: 0.015

A3:

B1: 0.046

B2: 0.094

C1: 0.008

LAWC35

ALK limited

Na2O at 5.4 wt%

LAW Correlation Multiple melter tests to underpin the waste loading

DM100

LAW Pilot

DM3300

0.12 m2

3.3 m2

1.2

%

1/3

DM1200 1.2 m2

12

%


10

• Concentrations of oxides of Al, B, Fe, Ti, Zn, Zr are fixed

• Waste composition (Na, S, K) determines sodium loading

• Sodium loading determines Li, Ca, and Mg oxide concentrations

• Silica is added to make composition total 100%

Oxides Al2O3 B2O3 Fe2O3 TiO2 ZnO ZrO2

Fixed Concentration

Value (Wt%) 6.1 10.0 5.5 1.4 3.5 3.0

Li2O calculated CaO calculated MgO calculated

0 to 4.3 wt% 2 to 7 wt% 1.48 to 2.97 wt%

0

1

2

3

4

5

5 6 7 8 9 1011121314151617181920

Li 2

O w

t%

ALK wt%

No lithium

beyond

18.15 wt% ALK

1

2

3

4

5

6

7

8

5 6 7 8 9 101112131415161718192021

Ca

O w

t%

ALK wt%

1.01.21.41.61.82.02.22.42.62.83.0

5 6 7 8 9 101112131415161718192021

Mg

O w

t%

ALK wt%

LAW Correlation:

7.0

75.12

4.5

2

2

1*3.4

ALK 1

)]2/)17exp((1[5.55.1

ALK1

)]9exp(1[49.148.1

ALK


11

WTP Correlation Tested in DM100 (also reflects +2σ limits for sodium, potassium and sulfate)

0

5

10

15

20

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

Na

2O

wt%

SO3 wt%

Correlation

Glasses proposed for testing

Actual Glass LAWEH Tested

Na2O at 5.4 wt%

20.8 wt%

19.8 wt%

Na2O LAW Pilot

DM3300

No separate layer

Production rate

~ 2000 Kg/m2/day


Office of River Protection is examining options to optimize the LAW facility and LAW glass waste form:

• increasing the waste loading

• Increasing the processing temperature

• Increasing the fraction of sulfur partitioned to the off-gas

12

ORP LAW Formulation Enhancement


13

ORP LAW Formulation Enhancement

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6

Na

2O

w

t%

SO3 wt%

ORP-S

ORP-A

ORP-B

ORP-C

ORP-D

ORP-E

ORP-F

ORP-G

LORPM

A B

C D

E

G (+5.4 wt% K2O)

F

LAWA-S

LAWB-S

LAWC-S

New

additives:

• Cr2O3

(K-3)

• SnO2

(VHT)

• V2O5

(SO3 sol.)


14

5

10

15

20

25

0.10 0.30 0.50 0.70 0.90 1.10 1.30 1.50 1.70

AL

K (

Na

2O

+ 0

.6 K

2O

) (w

t%)

SO3 (wt%)

Correlation 2004

Correlation Melter

testsORP 2005

ORP 2006

ORP 2007

ORP 2008

LAWA187

ORPLE12

ORPLD1

ORPLB4

ORPLA15

LAWC100

LAWA161

ORPLC5

LAWB99

ORPLD6

ORPLA20 ORPLG9

ORPLF7

ORPLG27 ORPLA38-1

ORP LAW Design and DM10 tests DM10


15

5

10

15

20

25

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8

AL

K (

Na

2O

+ 0

.66

K2O

), w

t%

SO3, wt%

Baseline Melter tests WTP Correlation Melter Tests

WTP Correlation Design ORP Melter Tests

Initial ORP Enhanced Correlation Design

Tank

AN-104

Tank

AN-105

Tank

AN-107

Tank

AZ-102

Tank

AZ-101

Tank

AP-101

Tank

AN-102

Alkali Limited Region

G A B

C

D

E

F

ORP LAW Enhanced Correlation: Waste Loading


16

0

2

4

6

8

10

12

0.6 0.8 1.0 1.2 1.4 1.6

Ca

O (

wt%

)

SO3 (wt%)

Existing ORP Glasses ORLEC-Phase 1 to Phase 3

ORP LAW

Enhanced Correlation:

Additives

12 additives

only 3 kept constant.

5

6

7

8

9

10

11

10 12 14 16 18 20 22 24 26

Al 2

O3 (

wt%

)

Alk (wt%)

Existing ORP Glasses ORLEC WTP


17

0.0

2.0

4.0

6.0

8.0

10.0

12.0

14.0

16.0

18.0

20.0

22.0

24.0

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

Na

2O

(w

t%)

SO3 (wt%)

ORP DM10 tests

177 tanks in TFCOUP

Four Correlation DM100 Phase 1

Four Correlation DM100 Phase 2

Five Correlation DM100 Phase 3

ORLEC33

ORLEC34

ORLEC44

ORLEC46

ORLEC48

ORLEC12

ORLEC26

ORLEC28

ORLEC27

ORLEC14

ORLEC16

ORLEC19

ORLEC22

ORP LAW Enhanced Correlation: DM100

• No formation of secondary layer

• Production ~2200 Kg/m2/d except ORLEC14 - ORLEC33


18

1150

oC

600oC

Box Furnace

1

2

1

3

1

700

750

800

850

900

950

1000

1050

0 1 2 3

Distance above bottom of crucible (cm)

Tem

peratu

re

oC

Bottom of crucible

1cm above bottom

2cm above bottom

3cm above bottom

Vertical Gradient Furnace (VGF)

1: Crucible

2: 10 g. of glass pre-melted

+ dried melter feed to yield 17 g. of glass


19

ID ORLEC14

(QWV-F-77A) ORLEC16

(PWV-F-133A) ORLEC33 (RWV-F-9A)

ORLEC50-F ORLEC14-OX

15

min

To

p V

iew

15

min

Cro

ss S

ecti

on

ID ORLEC53-F ORLEC56-F ORLEC57-F ORLEC62-F ORLEC65-F

15 m

in T

op V

iew

15 m

in C

ross

Sec

tion

VGF

evaluation of

LAW feeds Glass ID Oxides O

RLE

C5

0

OR

LEC

53

OR

LEC

56

OR

LEC

57

OR

LEC

62

OR

LEC

65

Al2O3 10.0 10.0 9.0 9.0 7.6 7.6

B2O3 11.0 10.0 11.0 10.0 10.0 11.0

V2O5 0.90 1.55 1.55 1.55 1.55 1.55

ZrO2 6.03 5.53 5.53 5.03 5.03 5.03

All at 1.0 wt% SnO2 vs. ORLEC14 2.33 wt% SnO2


20

ORLEC14 ORLEC33 ORLEC50 ORLEC56 ORLEC62

VGF: evidence of foaming


21

0

50

100

150

200

250

300

350

400

450

500

550

600

650

700

750

800

850

900

950

1000

1050

1100

950 1000 1050 1100 1150 1200 1250

Vis

cosi

ty (

Pois

e)

Temperature (°C)

ORLEC66

ORLEC67

ORLEC56

ORLEC65

ORLEC52

ORLEC51

ORLEC63

ORLEC59

ORLEC62

ORLEC64

ORLEC57

ORLEC60

ORLEC58

ORLEC53

ORLEC33

ORLEC61

ORLEC54R

ORLEC55R

ORLEC50

ORLEC19

ORLEC14

ORLEC56

ORLEC62

ORLEC50

ORLEC14

Temperature

dependence

of the Melt

viscosity


22

0

5

10

15

20

25

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

Na

2O

(w

t%)

SO3 (wt%)

ORP DM10 tests

177 tanks in TFCOUP

Four recommended for DM100 Phase 1

Four recommended for DM100 Phase 2

Five recommended for DM100 Phase 3

ORLEC33

ORLEC34

ORLEC44

ORLEC46

ORLEC48

ORLEC14

ORLEC50

ORLEC56

ORLEC62

DM100 testing: 4 glasses tested on same waste

ORLEC14: 1900 Kg/m2/day





• Successfully defined a new Enhanced LAW Glass Correlation.

• Established upper limits of waste loading achievable in LAW (Na2O, K2O, SO3).

• Acceptable glass formulations for vitrification which meet product quality (VHT, PCT, crystallization) and processability (melt viscosity and electrical conductivity, refractory corrosion).

• VGF was successful at scoping improved processing characteristics formulations, confirmed in DM100 tests.

23

Conclusions


24

Questions?

Dr. A. Kruger is gratefully acknowledged for the financial

support provided by the U.S. Department of Energy (DOE)

Office of River Protection.

Thank you to all my colleagues of the Vitreous State

Laboratory at The Catholic University of America

I. Pegg, K. Matlack, H. Gan, M. Chaudhuri, A. Kidder, C.

Wang, W. Zhao, J.B. Martin and the melter operators' team.

Processability of High Waste Loading Hanford LAW Feeds

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