D PST-84-556

Sludge Composition for Each Tank and DWPF Feed Batches

by J. R. Fowler E. 1. du Pont de Nemours and Company Savannah River Site Aiken, South Carolina 29808

MASTER DOE Contract No.

This paper was prepared in connection with work done under the above contract number with the U. S. Department of Energy. By acceptance of this paper, the publisher and/or recipient acknowledges the U. S. Government's right to retain a nonexclusive, royalty-free license in and to any copyright covering this paper, along with the right to reproduce and to authorize others to reproduce all or part of the copyrighted paper.

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Portions of this document may be illegible electronic image products. Images are produced from the best available original document

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M. D. . B o e r s m a , 676-T . . '

July 5 , 1984 I .

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J. T . GRANAGHAN, PLANT MANAGER SAVANNAH R I V E R PLANT I

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:!3 -... . . A T T E N T I O N : D. C . N I C H O L S ( 5 ) ... .

. SLUDGE :COMPOSITION FOR EACH TANK. AND DWPF .FEED BATCHES , ,

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TECHNICAL D I V I S I O N SAVANNAH R I V E R LABORATORY

. cc: DPST- 84-5 56

W. R. S t e v e n s , 111, 773-A G. W. Wilds , 77-3-A E. L. Albenes ius , 77-3-A R. B. Ferguson, 773-A M. A. Ebra, 773-A (3) M. J. P l o d i n e c , 773-A (3) D. C. W i t t , 676-1T D. G. K i l p a t r i c k , 676-1T R. E. Edwards, 704-T - L. F. Landon, 704-T B. G. K i t chen , 773-29A W. R. McDonnell, 773-418 TKS F i l e

J u n e 11, 1984

TO: M. D. BOERSMA, 676-T

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I,--- q! ,c 2: FROM: J . R. FOWLER, 704-T ( 2 ) .. 2 '.q ..,<-' .

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SLUDGE COMPOSITION FOR EACH TANK AND DWPF FEED BATCHES.

Summary

The chemica l compos i t ions o f s l u d g e on a tank-by-tank basis and i n t h e proposed f irst f o u r ba t ches o f f e e d to t h e Defense Waste p r o c e s s i n g F a c i l i t y (DWPF) have been c a l c u l a t e d . Chemical compos i t ions o f major t y p e s o f waste, based on a n a l y t i c a l and t h e o r e t i c a l work, were . p r e v i o u s l y estimated.ly2 These were used , a l o n g w i t h t a n k h i ' s t o r i e s . and c u r r e n t i n v e n t o r i e d to c a l c u l a t e t a n k compos i t ions . 'These i n t u r n were used , a l o n g w i t h b l e n d i n g t r a t e g i e s proposed by Interim Waste Management (WMWWMT)!, t o calculate t h e chemica l compos i t ions of ' the f i r s t f o u r batches of s l u d g e feed f o r t h e DWPF. These f o u r batches w i l l p r o v i d e abou t e i g h t years o f feed for t h e DWPF. I n a l l cases, t h e weight percents o f d r y s o l i d s were c a l c u l a t e d by assuming 1.95 l b s of i n s o l u b l e s o l i d s are p r e s e n t i n a g a l l o n o f s e t t l e d s ludge .

.

M . D. BOERSMA - 2 - DPST-84-556 I

The chemical c o m p o s i t i o n s of t h e f o u r proposed b a t g h e s do n o t d i f f e r g r e a t l y from t h e b lended waste compos i t ion t h a t has s e r v e d as t h e basis f o r DWPF d e s i g n and f o r waste glass p r o d u c t e v a l u a t i o n s . These batches s h o u l d be w e l l - s u i t e d f o r p r o c e s s i n g i n t h e DWPF w i t h o u t a l t e r i n g t h e p r o c e s s as now des igned .

Based on t h e b l e n d i n g s t r a t e g y and t h e age o f t h e s l u d g e i n i n v e n t o r y , t h e minimum age o f t h e - s l u d g e f e d th rough 1996 would be a p p r o x i m a t e l y 10 years a t t h e time o f p r o c e s s i n g t h r o u g h t h e DWPF. Most o f t h e s l u d g e would be a t l eas t 2 0 - y e a r s o l d a t t h e time o f p r o c e s s i n g . Because o f t h e age of these batches, r a d i o n u c l i d e c o n c e n t r a t i o n and s h i e l d i n g w i l l be o f m i n i m a l conce rn u n t i l a f t e r these batches a r e p r o c e s s e d . The a g e and compos i t ion of two a d d i t i o n a l batches w i l l be p rov ided by WMO/WMT t o e s t a b l i s h i f r a d i o n u c l i d e c o n c e n t r a t i o n and s h i e l d i n g w i l l be o f conce rn a f t e r t h e o l d e r s l u d g e i n v e n t o r y is d e p l e t e d .

Mercury is p r e s e n t i n a l l s l u d g e t y p e s a n a l y z e d t o date and is a l s o present i n s a l t . P r e p a r i n g a s l u d g e b l e n d f r ee o f mercury f o r t h e i n i t i a l batch t o be f e d t o t h e DWPF is p r o b a b l y n o t feas ib le .

Details

I. Tank- by- Ta n k Chem i cal Compos i ti on

A. Waste I n v e n t o r y and Composi t ion

Based o n - t a n k h i s t o r i e s , . Purex HAW and Purex LAW s l u d g e are segregated i n F-Area waste t a n k s excep t f o r Tank 7F. T a n k 7F has been used as a r e c e i v e r f o r LAW. The 'Purex HAW t h a t was removed from T a n k s l F , 2F, and 3F t o e n a b l e s a l t s t o r a g e was placed i n T a n k 7F. Based o n i t s h i s t o r y , T a n k 7F i n F Area c o n t a i n s a b l e n d o f Purex HAW, Purex LAW, s and a n d c o a l . S ludge volumes by t y p e f o r F-Area waste t a n k s are shown i n T a b l e I.

I'n H Area, s e v e r a l t a n k s c o n t a i n v a r i o u s b l e n d s o f Purex HAW, Purex LAW, HM HAW, a n d HM LAW because two p r o c e s s e s (Purex and HM) have been run i n t h e H-Area Canyon. Frame waste from Pu-238 p r o d u c t i o n is combined wi.th HM LAW waste. S e v e r a l s l u d g e t r a n s f e r s between '

. o l d e r t a n k s h.ave a l s o beei done d u r i n g i n t e r i m waste management . , o p e r a t i o n s . maintained i n t h e newer t a n k s . S ludge volumes by t y p e f o r H-Area waste t a n k s are shown i n T a b l e 11.

S e g r e g a t i o n o f HM.HAW and HM LAW s l u d g e h a s been

' .

M. D. BOERSMA - 3 -

B. Mercury Con ten t o f S ludge . ,

DPST-84-55 6

A v a i l a b l e results f o r mercury from specif ic s l u d g e samples a r e shown i t 7 T a b l e I11 f o r i n d i v i d u a l t a n k s . F-Area waste i s s i g n i f i c a n t l y lower i n mercury t h a n H-Area waste, b u t t h e waste i s n o t f r ee o f mercury.

C. Tanks C o n t a i n i n g One Type o f S l u d g e

Tanks c o n t a i n i n g o n l y one t y p e of s l u d g e are ,summarized below by waste type . Several t a n k s a l s o c o n t a i n s l u d g e s o l i d s from o t h e r o p e r a t i o n s ( z e o l i t e from CRC, s l u d g e from 100 Areas d i sa s sembly b a s i n s ) . These tanks are shown s e p a r a t e l y .

Purex HAW: l F , 2F, 3F , ' 4F, 5F, 6F, gH, 1 0 H , 33F; 34F.

Purex LAW: 8F, 17F.; 1 8 ~ , 19F, 20F, 47F.

HM HAW: 32H, '35H, 39H.

HM LAW: 2 1 H , 22H, 43H.

Zeol i te : 19F, 27F, 24H,' 42H..

. 100 Areas Sludge: 4°F.

The chemical compos i t ion o f each waste t y p e i s shown i n Table I V . Zeol i te , c o a l and sand - components i n spec i f ic tank,s o n l y - have been e l i m i n a t e d from t h e LAW e o m p o s i t i o n s t o p r o v i d e a d j u s t e d Pure-x LAW and HM LAW compos i t ions . The cornpas i t ion shown f o r HM HAW does n o t re f lec t aluminum d i s s o l v i n g .

D . Tan k- by-Tan k Compos i ti on s

C a l c u l a t e d c o m p o s i t i o n of s l u d g e s i n t a n k s c o n t a i n i n g m i x t u r e s o f s e v e r a l waste t y p e s are shown i n T a b l e s V - 1 t h rough V-3 . These compos i t ions i n c l u d e z e o l i t e , s and and c o a l where a p p r o p r i a k e .

11. Composi t ion o f DWPF Feed Batches'

A. Proposed B lend ing S t r a t e g y

The b l e n d i n g s t r a t e g y proposed by WMO/WMT is summarized i n T a b l e , V I . The volumes a n d c o m p o s i t i o n s shown assume that. t h e z e o l i t e p r e s e n t l y i n Tank 24H w i l l be s p l i t be tween Tank 1 3 H and T a n k 438. The z e o l i t e i n Tank 19F w i l l b e . t r ans fe r r ed to Tank 1 8 ~ . These transfers w i l l o c c u r b e f o r e DWPF feed p r e p a r a t i o n b e g i n s .

M. D. BOERSMA - 4. .- DPST-84-556

All s l u d g e s c o n t a i n i n g s i g n i f i c a n t amounts o f HM HAW w i l l be aluminum d i s s o l v e d . These s l u d g e s a re presently c o n t a i n e d i n Tanks 11H, 12H, 13H, 1 4 H , 15H, 32H, 35H, and 39H. The s l u d g e i n T a n k 42H h a s a l r e a d y been aluminum d i s s o l v e d .

R e s i d u a l volume o f s l u d g e a f t e r aluminum d i s s o l v i n g i s assumed t o be 50% o f t h e present volume i n i n v e n t o r y based on e x p e r i e n c e from t h e i n - t a n k d e m o n s t r a t i o n o f aluminum d i s s o l v i n g . Because o f t h e s i g n i f i c a n t q u a n t i t y o f o t h e r s l u d g e t y p e s i n T a n k 1 3 H , r e s i d u a l volume of s l u d g e from T a n k 1 3 H i s assumed t o be 75% of t h e p r e s e n t i n v e n t o r y . These a s sumpt ions were used t o estimate t h e volumes o f t h e f o u r batches t o be f ed t o t h e DWPF. I

B. Composi t ion o f DWPF Feed Batches

The major components o f t h e f o u r batches t o be fed t o t h e DWPF are shown i n Tab le VII. For compar ison , t h e compos i t ion of t h e o v e r a l l s l u d g e b l e n d p r e s e n t l y used i n t h e f l o w s h e e t is a l s o shown. These ba tch c o m p o s i t i o n s do n o t d i f f e r wide ly from t h e o v e r a l l s l u d g e b l end a n d t h e v a r i a t i o n s from t h e b l e n d s h o u l d have m i n i m a l impact on t h e d e s i g n and o p e r a t i o n o f t h e DWPF. s l u d g e s l i s t e d i n t h e p r e v i o u s s e c t i o n i s re f lec ted i n these compos i t ions . 'A comple t e l i s t i n g o f t h e components i n each ba tch i s a v a i l a b l e from J. R. Fowler , i f needed.

Aluminum d i s s o l v i n g o f HM HAW

111. Q u a l i t y Assurance a n d Q u a l i t y o f Data

R e s u l t s p r e s e n t e d h e r e are based on t h e bes t a v a i l a b l e data a t t h e time of w r i t i n g . f o r s l u d g e p r o c e s s i n g s t r a t e g y i n t h e t a n k farm. s h o u l d n o t be ' c o n s t r u e d t o y i e l d a n e x a c t d e s c r i p t i o n o f any s l u d g e from t h e t a n k farm b e c a u s e o f t h e v a r i a b l e n a t u r e o f waste h a n d l i n g and s i m p l i f y i n g a s s u m p t i o n s used i n t h e s e c a l c u l a t i o n s . p r e s e n t e d is o f s u f f i c i e n t a c c u r a c y f o r p l a n n i n g pu rposes , but i t w i l l n o t s u b s t i t u t e f o r a c t u a l analyses o f v a r i o u s s l u d g e samples d u r i n g s l u d g e removal and b l e n d i n g o p e r a t i o n s .

S ludge volume data ra ther t h a n weight data is a v a i l a b l e from T a n k Farm r e c o r d s . Consequen t ly , v a r i a t i o n o f t h e we igh t o f s l u d g e s o l i d s i n a s p e c i f i e d volume can i n f l u e n c e c a l c u l a t i o n s s i g n i f i c a n t l y . R e s u l t s from c a l c u l a t i o n s shown here are s t r o n g l y d e p e n d e n t on two s i m p l i f y i n g a s s u m p t i o n s :

The pu rpose o f t h i s document is to p r o v i d e g u i d a n c e R e s u l t s shown h e r e

Data

o 1 .95 l b s s l u d g e s o l i d s / g a l l o n o 50% r e d u c t i o n i n . s l u d g e volume d u r i n g aluminum d i s s o l v i n g .

M. D. BOERSMA - 5 - DPST-8 4-556

The volume o f 1 .95 l b s / g a l l o n has been used i n a l l s l u d g e compos i t ion c a l c u l a t i o n s a s s o c i a t e d w i t h t h e T a n k Farm a n d DWPF. - E x p e r i m e n t a l l y , s e t t l e d s l u d g e s o l i d s r a n g i n g from 1 . 5 . t o 2.8 l b s / g a l l o n have been

I n t h e i n - t a n k d e m o n s t r a t i o n o f aluminum d i s s o l v i n g , r e s i d u a l s l u d g e a f t e r treatment s e t t l e d t o a p p r o x i m a t e l y h a l f t h e o r i g i n a l volume o f s l u d g e t h a t was treated: be aluminum . d i s s o l v e d was used t o estimate batch s i z e s e x c e p t f o r T a n k l 3 H . s i g n i f i c a n t f r a c t i o n o f t h i s s l u d g e does n o t c o n t a i n a h i g h c o n c e n t r a t i o n o f aluminum hydroxide .

I obse rved i n samples from t h e T a n k Farm.

Accord ing ly , 50% o f t h e volume o f s l u d g e t o

Only 25% volume r e d u c t i o n was assumed f o r 1 3 H because a

References

1. R. E. E i b l i n g and J. R. Fowler , W p d a t e d Waste Composi t ion a t t h e Savannah ,River P l a n t " , DPST-83-313, Februa ry 1 6 , 1983.

2. R . E. E i b l i n g a n d J . R. Fowler , "Waste Composi t ion a t t h e Savannah R i v e r P l a n t " , DPST-82-897, October 4, 1982.

I I

3 . llMonthly Repor t - Februa ry 1984; Waste Management Technology",

4.

March' 5 , 1984.

S. J.' C a t h e y and P. .J. S h i p p e y , p r i v a t e communications.

J R F : t k s A t t

. TABLE I

SLUDGE I N F-AREA WASTE T A N K S

WASTE VOLUME (GALLONS) Ref. ( 2 )

I Purex HM HM T o t a l LAW HAW LAW Other , S l u d g e S a l t Pur ex

Waste Type: HAW

Tank No.

1 F 2 F* 3F 4 F* 5F* I

6 F* 7F* 8 F*

17 F* 18 F* 19F* 20F 25F 26F 27F 28F 3 3F

* 34F 4 4F 45F 46F 47F

7*0E3 4.03E r

4.0E3 1.3E5 4 . iE4 2.5E4 8.1E4 I l . 4E5

2.4E5 . 3.4E5 ,

2.7E5 2.5E4 1.OE4.

1.5E5

2.4E4 4.4E4

NOT I N S E R V I C E

* = s l u d g e sampled a n d a n a l y z e d .

1.3E5

7*0E3 -4.OE3 4.OE3 1.335 4.1E4 2.534

S i O 2 , C 2.235 2.4E5

> , '3.4E5 . 2.7E5

z e o l i t e 2.5E4 1.OE4

'1.5E5 z e o l i t e

2.4E4 4.4E4

100 Area 1.3E5

..

- 4.3E5 4.5E5 4.3E5

'3 .4E4

3.835

2.OE4'

4.OE5 3*7E5

l . l E 5 9.2E5

1.7E5 4.9E5 1.5E5

5.3315 ~

2.4E5

TABLE I1

SLUDGE IN H-AREA WASTE TANKS

.WASTE VOLUME (GALLONS) Ref. ( 2 )

Purex HAW

Purex LAW

HM HAW Other

T o t a l Slud.ge

HM LAW S a l t Waste Type:

Tank No.

4.OE3 4.OE3

6.0E4 1 . 4 E 5 1.7E4

4.0e3 4.OE.3 1.8E5

‘2 .5E5 % 4.OE5

2.7E4 2.735

9H* . 1 0 H *

1 1 H * 12 H* 1 3 H * 14H 15 H* ’16H* 2 1 H 22H 23H* 24H* 29H 30H ’

3 1 H

1.5E4

.5.OE3

1.6E5

1.9E5 _ I l . 9 E 5

5.0e3

6.8E4 1.0e4 4.0E3 . 2; 7E5

SLUDGE TRANSFERRED TO 15H 2.2E5 5.3E4 4.3E4

2.235 5.3E4

4.3E4 z e o l i t e

RBOF WASTE: DPST-84-342 SHOWS ANALYSIS

1. O E ~ 6.0e3 9.635

1.3315 3.5E4

1.3E5 3.5E4

3 2 H 3 5H

’ 3.635 3.1E5 36H

3 7H 38H 3 9H 40H 41 H 42H

48H 4 9H 50H

43H

\

, 5.OE3 5.OE3 8.4E4

g.OE4

PRECIPITATION PROCESSING T A N K

z e o l i t e 9.0e4 2 .‘4E4 2.4E4

* = s l u d g e s a m p l e d and a n a l y z e d . - ..

Tank No.

1F 2F 3F 4F 5F 6F 7F 8F 17 F 1 8 ~ 19F 20F 25F 26F 27F 2 8 ~ 3 3F 34F 4 4F 45F 46F 47F

\

TABLE I11

MERCURIC OXIDE I N SLUDGE SAMPLES

,Wt. % HgO 0.024

-0.19 ,

0.12 0.19 0.076 0.11

0.11 0.072

Tank No.

9H 10H 11H 12H

. 13H l4H 15 H 16H 21H 2 2H 23H 24H '29H 30H 31H 3 2H 35H 36H

39H 40H 41H . 42H

' . 48H 4 9H 50H

%:: 43H -

Wt. % IIgo

3.6 1.2 2.5

4.3 3.0

I .

NOTE: R e s u l t s f o r t a n k s 1F a n d 1gF are on'insoluble r e s i d u e from 1 salt samples .

. TABLE IV

SLUDGE C O M P O S I T I O N BY WASTE (WT X O F ECSCH SPECIES)

Xef (1) - sludge AUJUSTEDd.

species F'UREX HAW F'UREX LAW PURE)! LAW HM Hfi

TYPE'

I HE .L ADJUSTED$

HM LAW w

Fe ( O l l j 3

UO2 (OH) 2 R1 ( O H 1 3 CaC03 C&04 CaC2D4 Ca3 (PO4 1 2 CaF2 I\li ( O H 1 2 NaClH NEINOS Ily 0 NaC1 Na I KL1132 Si 552 Tho2 B a s 0 4 Ce ( O H j 3 F'bSO4.

, , I -a (OH13 ZlCO (OH) 2 C r <OH> 3 AgOH cu (OH 1 2 Ca (OH) 3 I ' r (OH) 3 Z n (01-4) 2 Mq (OH> 2 COAL ZEQLITE t:::NO3 l\la2S04* KOIi srco3 BaC03 F&CO3 N a 2C2O 4 N a3P04. NaF SAND

' I lr iQZ

% 'Zeolite, coal and sand suht rac ted frori! t a k a 1 and weight p e r c e n t rexdjusted.

T A B L E V - 1

PbS04 L a ( 011 1 3 Z r O ( O i l ) 2 C r COEI) 3 RyOH CU (OH 1 2 Ca (OH) 3 Pr (ON) 3 Z n (OH) 2 Mg 101-1) 2 COCSL Z E O L I TE Kl\l03 Na2rSO4 KQII S r C 0 3 BaC03 PbCrJ3 Na2C2U4 N a3 P O 4 NaF SAND

I

. . 0

I I

I I

I I

I I

I I

I I .

I I

.- I '

I I

I I

I I I I

I I

I

I I

I I

1 I

I I

I

I I

I I I

I I

I I

I I

I

I I

I I

I I

I I

I

I I

I I I I I I

I I

1 I I I I I

I I

I I

I

\

TABLE V I

Ba tch Number

la

2a

3a

SLUDGE BATCHES FOR FEED TO THE DWPF SLUDGE PLANT Ref (3 )

T a n k Waste Number ’ Type

. 1 8 ~ 21,22H 4 2H 1 9 F .

1 8 ~ 15H 1 1 H l 4 H 1 9 F

12H 5F 6F 7F 7F 8F 8F 8F

P-LAW HM-LAW HM-HAW ZEO.

P-LAW HM-HAW HM-HAW HM-HAW ZEO.

HM-HAW P-HAW P-HAW P-.HAW P-LAW P-HAW P-LAW P-LAW

Waste Age

16Y 13Y 25Y ---

27Y 3 2Y 27Y. 39y . 3 1 Y 24Y 37y 1 5 Y

Waste Volume

Cumulat ive Volume

227,000 227,000 311,000 538,000

91,000 . 629,000 ? - 629,000

I .

410,000 .269,000. 176,000

27,000 ?

253,000 41,000 25,000

175,000 46,000

118,000 59,000 59 ,000 .

Year Fed t o DWPF

89-90

91-92 410,000 544,500 632,500 646,000 646,000

93-94 126,500 167,500 192,500 367,500 413,500 531,500 590,500 649,500

4a 4F 1 3 H 13H 13H 13H 26F 2 4 H

P-HAW P-HAW P-HAW HM-HAW HM-LAW P-LAW ZEO.

26Y 40Y 4 l Y 3 2y 33y ->5Y

127,000 175,000

40,000 80,000

108,000 20 0 , 000

?

127,000 258,250 288,250 348;250 429,250 629,250 629,250

95-96

S l u d g e Species

Fe(OH)3 Mn02 U02 (OH 2 Al(OHI3 CaC03 CaF2 N i ( O H 1 2 N a O H NaN03 Na2SO4 NaF NaCl NaI H g O Ru02 S i 0 2 Coal Z e o l i t e Other

T o t a l

G a l l o n s of Feed

F-Area T a n k s

H-Area T a n k s

TABLE V I 1

COMPARISON OF DWPF FEED BATCHES TO OVERALL BLEND

Batch l a ( W t % >

42.68 8.07 5.46

19.92 '4.19 0.12 1.86 3.68 1.67 0.09 0.07 1.45 0.. 01 1 - 9 5 0.25 2.03 0 0 .81 5.68

100.00 '

629,000

18

2 1 , 2 2 , 4 2

Batch 2a ( W t % )

37.49 4 .,5 3 5.79 .

20.88 3.42 0.21 2.90 3.93 3 - 3 5 0.23 0.17 1.30 0.03 - 2.23 0.45

' 4.58 0 1.18 7.33

100.00

646,000

18

1 1 , 1 4 , 1 5

Batch 3a* ( W t % >

42.33 8.66 8.38 .

,13.50 2.87 0.11 4 .41 4.46 2.38 0.13 0.09 0.63 0.01 1.32 0.39 2.81 0.54 0 6.99 '

100.00

649,000

12

Batch 4a ( W t X )

41.90 7.89 7.56

12.59 3.43 0.13 3.62 4.14 1.66 0.06 0 .'04 0. 95 0.01 0 .91 0.38 1,83 0 7.54 5.35

100.00

629,000

4,26

13

39.89 6.84 6.63

16.. 4 6 3.38 0.15 3.16 3.98 2.34 0.14 0.10 1.07 0.02 1 .60 0.37 2 .94 0.13 4.50 6.30

10 0'. 0 0

B 1 e n d* * ( W t % 1

* I n c l u d e s s l u d g e from Tank 7F

**After DPST-83-313