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,TECANICAL DIVISIONSAVANNAH RIVER LAB03ArORY

MEMORANDUM

.. . .

IJ REc~~mlON’DPST-82-677

AYNP

J .4P!yM.$~ie~,g{i?~&cc:J. R. Hilley, SRLS. NirshakJ. A. KelleyR. M. WallaceE. L. AlbenesiusJ. F. OrtaldoM. D. BoersmaF. H. BrownM. A. EbraM. J. PlodinecD. C. WittW. V. WrightB. V. ChurnetskiL. M. LeeD. D. WalkerTIS File (2)—

July 6, 1982

. TO: R. B. FERGUSON~ls FILE

k, 1 ‘RECORL COPYFRoM:‘- >~~>

CESIUM REMOVAL FROM SYNTHETIC SUPERNATE USING DUOLITE CS-1OO

INTRODUCTION

This document describes a laboratory tracer facility whichwas used to show Duolite CS-1OO resin’s capability for removingcesium from supernate. The data presented is part of the HighLevel Waste Technology Section’s effort to develop designinformation for the Reference Defense Waste Processing Facility(DWPF ).

.

.

.-( .!):..,, .,.

DPST-82-677R. B. FERGUSON 2 JUIY 6, 1982

BACKGROUND

About 20 million gallons of high level radioactive waste,generated in the production of special nuclear materials duringthe last twenty-five years, are stored in large underground tanksat the Savannah River Plant in the form of a damp salt cake and agelatinous sludge. A process was being developed1~2*3r4v5to: (1) remove from supernate the hazardous radionuclides, (2)recombine radionuclides with sludge, and (3) combine sl~udge inleach resistant glass matrix suitable for long-term geologicstorage. A step in this conceptual process is the use of an ionexchange resin to remove cesium from the supernate.

suMMARY

A tracer facility (Figure 1,2) for testing ion exchangeresins was built and used to test Duolite CS-1OO resinjscapability to remove cesium from synthetic supernate. Cesium-137was used as a tracer. The variables, feed flow rate, and cesiumconcentration were plotted as functions of, % change of cesiumconcentration to column volumes passed ‘(Appendix A). Theresultant Kd’S were then plotted as a function of cesium

.concentration (Figure 3) . The lZddata was then extrapolated toother hydroxide cesium concentrations, (Appendix B) .

.. At a DF of 10,000, the relationship of feed flow rate wascorrelated to column volumes passed and cesium concentration(Figure 4).

The physical properties of the resin are shown in Appendix C.

I/E TRACER LNEL FACILITY (TLF) EQUIPMENT

The major goals of this equipment were to demonstrate theproposed DWPF flowsheet and to explore the I/E variables such asfeed rate, elutriant composition, and regenerant composition.

The height of the cesium I/E resin column (92 inches) was ;near the expected DWPF column height. A three inch diametercolumn was chosen to meet the limits of radiation and maximumreasonable laboratory feed tank size (100 gal.). A schematic ofthe I/E test facility (ST5-22530), as installed in the laboratory(Room 139, Building 7737A), is shown in Figure 1. The facilityincludes: ~ 91ass I/E column, lIJOgallon feed tank, receipt tankanti automatic gamma counting sensors in column input and outputstreams.

R. B. FERGUSON

Both columns wereat 50 psig. The resin

-,

DPST-82-6773 JUIY 6, 1982

made of Corning beaded pressure pipe ratedwas supported bv a Perforated Dlate. A

Johnson P~ofile wire screen (~~07 inch”slo~) distribu~ed the feedat the top of the column and prevented resin from entering thefeed line during the backwash cycle.

A mix tank (30 gal. stainless steel) was used to make upelutriant and regenerant. Polyethylene carboys .(50 liter) servedas metering tanks for water, elutriant, and regenerant.

Two mRoy duplex positive displacement pumps (maximum flow12.4 gph for load and 3.6 gph for elution and regeneration]supplied feeds to the column. Four Jabsco@ self-priming impellerPumps (5.5 gpm at 10 ft. head) transferred liquids from drums,metering tanks, receipt tank, and floor pans.

Over-pressure protection was provided by 35 psig reliefvalves on the metering pumps and by 30 psig electrical pumpoverpressure interlocks that: shut off the pumps, fed the tankagitator, and sent an alarm to Building Operations. The pumpswere also shut off by level switch/alarms that were activated if apump ran dry or liquid spilled into a secondary floor containerpan. See ST5-20550, 20552.

Because of the very low cesium-137 tracer concentration inthe I/E effluent, automatic counting equipment and 3 inch sodiumiodide detectors (in lead shielded counting chambers) were used.The I/E inlet feed chamber (44 ml) was made of a coiled 0.15 IDTeflon tube, and the effluent chamber (1000 ml) of teflon andpolypropylene (SK 3620-LS). These plastics were used to reducebuildup of radionuclides on surfaces and thus retiuce backgroundlevels and variations.

EXPERIMENTAL RESULTS

Duolite CS-1OO resin (Lot 316-300-OE; 40-60 mesh U. S.standard) in the hydrogen form was loaded in the column and thenconverted to the sodium form with 0.5 molar NaOH. Spiked super-nate was passed through the column (Table I, II, III and AppendixA) and the results tabulated (Table III, IV) and plotted (Figures3,4). The results were then extrapolated (Appendix B) to othercesium and hydroxide levels (Figure 5).

The feed and first rinse cycles were downflow, and theelution and regeneration cycles upflow. After loading the resinin the column, it was treated with elutriant and regenerant.Gamma counting of the process streams was used to calculate the

DPST-82-677R. B. FERGUSON 4 JUIY 6, 1982

decontamination factor (DF) and the elution frequency. The down-flow feed rate tested was varied from 0.43 to 3.0 gpm/ft2, andthe upflow elution-regeneration rate tested was 0.54 gpm/ft2.Elution of cesium was with .5 molar formic acid3 and regenera-tion with 0.5 molar NaOH.

The supernate pressure drop through resin is shown by Figure19 in Appendix C.

LLK :pmcAttDisc 1

,,

I 1

SUPERNATEWATER FEED

“f ‘J ; i

HIGH-LEVEL

COUNTE

REGEN-WATER

ELUTRi-ERANTNaOH

ANT

(~~=.tiWASTE d L BACKWASH

WATER

FIG t *“RN

STRONTIUM TRACER LEVEL 10N EXCHANGE FACILITY

R. B. FERGUSON

R—

sI

L

6

ti

DPS

,.,, , ,i., ,,

R. B. FERGUSON, ,7DPST-82-677JUIY 6, 1982

TABLE I

Synthetic Supernate Feed to Duolite CS-1OO Ion Exchange Column

Ion R

A1O ~ 0.423

NO~ 2.2

NOz 0.95

OH 1.62

co ~ 0.48

sol 0.24

LNa 5.3

SpGr = 1.29

Dissolved Solids = 33%

t

R. B. FERGUSON

123

456

789

DPST-82-677JUIY 6, 19828

TABLE II

CS-1OO Experimental Ranqe Attempteti

4C5C6C

7C8C9C

10CllC12C

RangeExpected gsKd Ly Cv ‘s/Hr

100 2.5E-4 1.7100 2.5E-4 3.8100 2.5E-4 .84

50 2.5E-3 1.750 2.5E-3 3.850 2.5E-3 .84

200 2.5E-5 1.7,200 2.5E-5 3.8200 2. 5E-5 .84

9P m/ft2

1.332.970.66

1.332.970.66

1.332.970.66

m, ...i

.,”, ~

DPST-82-677R. B. FERGUSON 9 JUIY 6, 1982

TABLE III

Distribution Coefficient (Kd) Measured at 60% ColumnBreakthrough

Test&

lC

2C

4C

SC

6C

7C

EC

.9c

10C

llC

12C

CV’ s/Hr

1.58

1.61

1.66

3.8

. 57

1.55

2.13

.51

1.5

2.0

.55

gsM

2. 4E-4

,,

,,

,,

,,

2.5E-3

,,

,,

2.5E-5

,,

0,

Cv’s@ 60%Breakthru

35

37

32

28

32

14

14

14

40

55

57

(1.1)

Cv’s~

38

40.7

35.2

30.8

35.2

15.4

15.4

15.4

44

60.5

62.7

KdSeeBelow

89.3

94.4

81.7

71.5

81.7

35.7

35.7

35.7

102

140

145

(1.l)(CV’S @ 60%) \ ~(_22 45 In ~s, - ~031‘d = (U.431) ;

(Figure 3)

@B= 0.431 gms resin in Na form/ml resin in Na form in lM–NaOH.

‘,

. .1

.“ .’

R. S. FERGUSON 11DPST-82-677July 6, 1982

TABLE IV

At DF = 10,000 Supernate Flow Rate vs. Column Volumns Fed AtVarious Cesium Concentrationst

Test*

8C

-lC

5c(2)

4C

2C

lc

6C.

llC

10C

12C

c Sfi

2.5E-3

2.5F,-3

2.5E-3

2.5E-4

2.5E-4

2.5E-4

2.5E-4

2.5E-4

2.5E-5

“2.5E-5

2.5E-5

Cv’s

21

23

41

10

18

19

21

26.5

21

23

41

CV’ s/Hr

2.13

1.55

.51

3.8

1.66

1.61

1.58

.57

2.0

1.5

.55

9Pm/ft2

1.66

1.21

0.40\

2.97

1.30

2.56

1.32

0.445

1.56

1.17

0.43

*See Appendix A.

,.

t

.,

., . .,,., DPST-82-677

J

.

.,

*

f., !, I I

,, ,U ,,, ,,, ! — I_L_:;_—l—!

R. B. FERGUSON 14

APPENDIX A

DPST-82-677JUIY 6, 1982

Experimental data plots are shown in the following figures.

The reasoning for plotting the experimental data is shown in

Figure 6. The data plots are shown in Figures 7 to 18. A

tabulation of the experiments run is shown in Table III.

#

R. B. FERGUSON 15

EXPERIMENTAL NOMENCLATURE

DPST-82-677July 6, 1982

F16 6

II I

Cv’s

v =Kd[P(l-@)] +9 - ~BCv’s ‘E

‘KP+fl

$ = volume fraction, liquid/bed volume.1P = density resin wet

c“ = volume of column.,

Cv’s = volume of feed

P(l-@) = bulk density of resin wet

let PBwt dried form

= bulk density = V. Ume ~n ~quld

= q/g =volume bed

‘d _ vo~ume teed

q = solid concentration, gm equal/ml bed volume

~ = liquid concentration, (g-equiv)/ml

~n Practice: PB ‘d %1.1 [(cv)’s at 60% breakthrul

. .!

... .,,.*

- ,.R. B. FERGUSON

DPST-82-67716 JUIY 6, 1982

——. ..—_— ..—.1:

..T-.... s-–--: ~--:~-~J -

—.

,,.,,.... ,,, , * DPST-82-677

b

.!

\.

,,

!“”-”l“--::’;’$ loo ;

s“”““ ‘“””””:3:90 ;

;_.-_$.... .._..._............~~ :

?+

.. ...3.. .@ :

. . . . ..z.. .... ~.:2 : : ~.-

~“”’”:’’’’:”k”’70 :,.:.q, :.... ,.

-......M-............. ...... .....!.....,;h ~ , ;---

;V:.2..........O ...... i..:.Q :

...-._.-....m.. .,:.., ./....”:..

---m;--, - , ~~~~!

-2 ,%

,:;:::!!.:

;,

L.......~!.. : j :““’’”-”;”””’qo” “’ ~~~ \ “*------- -...-:-.-...-/ ..... . .... ..... .... .... .. . .... ... ... ..

q :.~~ _:!

. . ...-~.$..........:..:.::._~.....zo---;~””;--’--- ~—._._.

;.. :,:, ,,, 1 ,COLVMN M1

I

~ .,. .. .. .. ..\....i... _...\::;

..:.

e —.1:.,

, .!,;,~.,, L DPST-82-677

R. B. FERGUSON 18 JUIV 6. 1982 Sb. l}.!,[7–ll,,:l:!:l-

.’, ...,,, ,, ...

...

. . ...,.?.. . .

J: ..].:.: . .. .

I I i .:@---- :!:..:,:4_~__J._.;.:+ ...!‘U ‘;: .-., ,,--.:.-. -: .:._ ,’--.+~!...j~j~ .~, I.:*.:gai:, ,,i:~:4J~.,L_.,._

..: !-J--O.2E:,:”,. f; i’ _ \,:..~. -1

7

,...,.~~,.

7

‘;,,,,:-:: --f ‘“” “

t-d --1:1’ d–”! ““““”’‘&”TKlw “1!W-””!:”’-’’l–””-”-–” fi”--fi %

. . .,+.

R. B. FERGUSONDPST-82-677

19 JULY 6, 1982 ~

—

.

DPST-82-677

‘+i+..i . . ..+. .1:,,... . . . . .: -i.: ...

.--~~’::

20

“’-”-’-1--- ““.—-.. ..

“’T””..:Q...- ~ : ..::-:. ;:7:.1:: I ,,

: l,:. /..i , l:.ii~j ,j

,.. ,!1 :!: ,,,:i; ,~

,:, :,—._, .._ l...._1 !

u

i 1:)’11,1:,. 1’11;1::!’1!.l: l:’ ,., , L I ! i 1. l..:,, ,,A

Iii !j&l,l Il i I .11 :..’11 $

o“U

x

w“

- -.

,..-...- / ~~ ‘ I.-,--a ....... .‘“””””:“”–-–T’-””– -”i-”:.: ‘-. ‘:-:-—T

C~L UNN VOLUP’4ES

., ..%* .

i. B. FERGUSONDPST-82-677

22 JUIY 6, 1982a... ,,., ,... . . . ,. a:.!. . . . . . i::”r:.::.a _

~, r,:

&,\/.[..,;...,.........—. , .. .._. -

,1,!.

: ,.. ,.

.;,.. ,

!!..,..

. ,..!—.—. .! . . . . . . . ...!. .. ... . . . ..:, _.. . !

I 4

,...

‘ “–-””l:”1’”‘;,.-..:j.:-~.:-..:..p...

,. I 1.’[”.1“’””’:?’:–:”’

1 ,.:.l..1..+—....!+..-...... ....-~ i: !,..i

,,

7

~,. .DPST-82-677

R. B. FERGUSON 23 JULY 6, 1982 ~

. . . ....! ,. , 1 .1.. :-.-1.. --: iI;,/1/1;1 ,. !:..:.l..... ..._/”...

;~-”j:””

-j:-.. -.!.......‘ I,.-----.......I

“’i’--”1!-”!- ~~1:

::i.~

~!

!II

~~ 1

-+-.... ... ..... .... ... .. ... .-,

,1 ..: ;.:.: :..,.,I : ../.

, l,,olf)~

$ .\

DPST-82-677>“ , .,

R. B. FERGUSON 24 JUIY 6, 1982.. . . . a,, .,.

‘“’-’-1

!. .:...R

. ~.-—- ~::;~:.... ~,’,

“+--~:fiqI /:

!-~” ,3

;,,— ..- . ‘~,..

i’l~~.l.. a

~,]

:“;’”’ -i””’:” :2;

:.

..,...-._— .-

,.

,. ...

‘.. .

.. . . . . ~.,

,.:.ti “~~”’ ‘Tj“”~’q--

;,..

:1

J....!..; i,.,.. .

,/

.&LL_. —---

,.

;,,!.

. -.

:[:,..

. . .,-,- ._.- l-~---i - -+--

;,..4 ..-.. -

;:.:: _\_:...—l:.-,,,

--.:...!.:_j_..~!...I,.. .Y._ :-..;....

:...}..-;.;

,;~.~,’:., ..

~,1.I

)“~i”d:I-----.—l,. !

—- .:.’.,.

.. ......!. .

. . . ..-

i... .. ; :..: ,,...

+- . . .~.:

:,i. .,

.. . ..—.. . . .. .:..

:.:1.:. . . .

: ..._+@

.-

,..,,

;..

--4

,, ..\.-. . ,.

DPST-82-677R. B. FERGUSON 25 , JUIY 6, 1982 ~

, ..,1

~ :

i:.,..

E..

.,, :.,, ,,,,,, ., :,-: ~g

. .../... L.. —.— ., —_:__

-;--+-I:-* j“,;;,:f@!,, ,,: ;

,, A.! . ,.

R. B. FERGUSONDPST-82-677

26 JUIY 6, 1982~:...-T-i:’;”a”:’\!’* , - ;... . ,,.,.. 3------dti

,.. i-- :---- !----4S

‘1

;.. .

,.-.

Y:: i +1+-+-l--:~--i - ~- .–.:-..::L.-i.::.!.::LJ.:: i..

I I I .1 Ii. . 1.!.1

-.:.~~:-~n-j:-.l: ij - I !’..—. 1...i I . . ... .....!......-d

- i-*t-2--—— f- ----r—--+ -—--~+-.

,,,,,,, ,,,, ,,,,,, .,,,, ,, ,,

DPST-82-677JUIY 6, 1982R. B. FERGUSON 28

APPENDIX B

Data relating the effect of cesium anti hydroxyl concentration

on the Kd of Duolite CS-1OO was measured by Eber4 and is shown

on Table VII. This data was fit to the fo

[ ,61,log K~= ..805 log CS + .263 + (.15

09 c~ -

lowing equation:

J(m)– (1)The Kd values measured in the Tracer Level Facility (Table

IV and Figure 3) were fit to the following equation:

‘d obs = (-22.451n(Cs)) - 103

The following equations were used to

at other cesium and hydroxide conditions:

Substituting 1 and 2 in 3, gives:

‘d =new

which was used

A general

(2)

predict the Kd value

(.15)(m)- [12.831n(Cs) + 58.91[10 1

(3)

(4)

to plot Figure 5.

case equation for extrapolating from any observed

Kd to a Kd at any new cesium or hydroxyl level was developed

from equations 1 and 3. t

,)

DPST-82-677R. B. FERGUSOS 29 JUIY 6, 1982

.‘dnew –

—

K~ob~ =>

Cs =new

OH =new

Cs =obs

OHobs =

predicted value of i’idbased on new Cs G OH

observed Kd at Cs and OH given

Cs molarity at predicted Kd

hydroxide molarity at predicted

cesium molarity at observed Kd

i(d

hydroxide molarity at observed Kd

‘dne~[(Kdobs)l

—

[

.805 log CS,new + .263+ .15 Gne

.161 log CS neW - 1.- iL u“

[

.805 log CS, + .263+ .15 Gobs

. 161 log CS, - 1 1T,-.Au —

(5)

..

R. B. FERGUSON 30DPST-82-677JUIY 6, 1982

TABLE V(Ref 4)

Kd, for Duolite CS-1OO at Various ~ and ~ Concentrations and6M Total Sodium

OH- Corig.c

-, eq (Kd’)*

4iY 1 x 10-1 8.49 x 10-2 13.3,, 1 x 10-2 6.00 X 10-3 49.8,, 1 x 10-3 3.59 x 10-4 134,, 1 x 10-4 2.94 X 10-5 179,, 1 x 10-5 1.16 X 10-6 568

2M 1 x 10-1 8.89 X 10-2 9.37

,, 1 x 10-2 6.83 X 10-3 34.4,, 1 x 10-3 4.92 X 10-4 77.1

,, 1 x 10-4 2.57 X 10-5 216

,s 1 x 10-5 1.33 x 10-6 486

.s lM 1 x 10-1 9.53 x 10-2 3.72

,, 1 x 10-2 8.02 X 10-3 18.5

,, 1 x 10-3 5.54 x 10-4 60.1

,, 1 x 10-4 3.39 x 10-5 146

,, 1 x 10-5 1.94 x 10-6 312

0, 1 x 10-6 1.32 X 10-7 492

,, 1 x 10-7 1.04 x 10-8 643

O.lM 1 x 10-1 9.62 X 10-2 3.00

,, 1 x 10-2 8.56 X 10-3 12.5

,, 1 x 10-3 6.66 x 10-4 37.5

,, 1 x 10-4 4.88 X 10-5 78.4

,, 1 x 10-5 3.48 X 10-6 140

,, 1 x 10-6 3.16 X 10-7 500

*

Based on bulk density = .413 = PB

L wt of oven dried Na form‘B VO1 Ot Na form ~n NaOH

R. B. FERGUSON 31DPST-82-677JuIY 6, 1982

APPENDIX C

TABLE VI?

Chemical & Physical Properties of Duolite CS-1OO

Property

Weiqht Ratios

‘1 air dried H+ ffrm/wet H+ form ‘1)0.681

:+‘2 wet Na+ form/wet U form ‘1)

1.502

‘3dry Na+ form/wet H+ form(l) 0.911

‘4 oven dried 3+ form/air dried 1-l+form1.09

Bulk Densities, g/ml

H+ form(2) 0.694

‘H

‘NalNa+ form ‘3) 0.515

PB Na + form(4) 0.413

Capacity

c(g) meq/ g(5) 3.65

C(V) meq/ml(6) 1.71

Lot NO. of resin 316-300-OE

(1) +H form as received from vendor.

(2)Weight of wet H+ form(l) /volume of H+ form in water.(3)Weight of wet H+ form ‘l)/volume of Na+ form in lM NaOH.(4)Weight of oven dried Na form/volume of Na+ form in lM NaOH.(5)Neq/g of dry Na+ form.(6)Meq/ml of Na+ fOrM in lM NaOH.

“, &!-.

.

R: B. FERGUSON 32DPST-82-677JUIY 6, 1982

.. ...

~;“ 9,6-a,

R.DPST-82-677

B. FERGUSON 33 JUIY 6, 1982

TABLE VII

Pressure Drop vs Flow Rate of Supernate (33% Salt) at 25°c(Load Cycle - 3“ Diameter column)

PressureTest DropNo lb/in2-

4C 3.67

3.96

5C(2) 9.4

6C I..o

10C 3.3

llC 5.1

psi/ft

HeightColumnInches

77.5

76.5

72.0

74.

73.

74

– 1.2412.

[1

.4518 ~ft

Flow RateCV’s/hr ~z

1.65 1.33

1.65 1.31

3.8 2.85

0.57 .439

1.5 1.14

1.9 ,1.46

x 9.6 81.3 2.87 2.42

psi/ft

.568

.621

1.567

.162

.542

.827

1.42

. .,

-\” F

R. B. FERGUSOE

REFERENCES

1.

2.

3.

4.

5.

34DPST-82-677JUIY 6, 1982

L. L. Kilpatrick, “Strontium Removal from SyntheticSupernate Using Amberlite IRC 718”.

“Preliminary Technical Data Summary for the Defense WasteProcessing Facility, Stage 2,”, DPSTD-79-38-2, Savannah RiverLaboratory, E. I. du Pent de Nemours & Co., Aiken, SouthCarolina (1981).

R. M. Wallace, “The Basis of an Improved DWPF Ion ExchangeProcess: Absorption of Cesium on Weak Acid Phenolic AcidResins, Duolite CS-1OO and S-761 and Elution with FormicAcid.”

M. A. Ebra, “Cesium Distribution Coefficients for CS-1OO atVarious OH- Concentration, 6M Total Na,” Monthly Su,mmary,January 1981.

L. M. Lee, “Decontamination of Dissolved Salt Solution fromTank 19F Using Duolite CS-1OO & Amberlite IRC 718 Resins,DPST-81-329, May 1, 1981.

. .,

.