results from tank 48h slurry decontamination and …/67531/metadc687350/... · from tank 49h to...

WSRC-TR-96-0190

Results from Tank 48H Slurry Decontamination andDecomposition Experiments in Support of ITP ProcessVerification Testing

by

D. D. Walker

Westinghouse Savannah River CompanySavannah River SiteAiken, South Carolina 29808

C. A. Nash

DOE Contract No. DE-AC09-89SRI 8035

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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●.,301 .%[/, 4’0057 ~“‘ ,.-

WESTINGHOUSE SAVANNAH RIVER COMPANY WSRC-TR-96-0190SAVANNAH RIVER TECHNOLOGY CENTER m

Keywords: In–tank process,flammability, benzene,tetraphenylborate

Retention time: permanent

September 6,,1996

TO: S. D. FINK, 773-A

FROM : D. D. WALKER, 773-A, and C. A. NASH, 676-lT

RESULTS FROM TANK 48H SLURRY DECONTAMINATION ANDDECOMPOSITION EXPERIMENTS IN SUPPORT OF ITP PROCESS

VERIFICATION TESTING (u)

Authors

i9-cs.hAJ-Q .(!.Jf@@L-i dd%————————...————————.—————————.—————D. D. Walker, Interim Waste Technology Section

———__._——Date

oLz’4A@A’iJL_ ------------------------- 6 d-----—————~. A. Nash, I~e=im Waste Technology Section , #& ate

&pTec nical Revi.ew

?/+L-~—_———————————___————————_——————————————M. . Barnes, Interim Waste Technology Section D te

Appro

&————

{

f fl~——————————————————————W. L. Tamosaitis, L&@ 3 Manager,. E–teInterim Waste Technology Seation

WSRC-TR-96-0190Page 2 of 35September 6, 1996

Summary

Addition of sodium tetraphenylborate (NaTPB) to Tank 48H willreduce the soluble CS–137 concentration to below 12 nCi/g, wellwithin the pending Process Requirement limit of 85 nCi/g. Additionof 175 gallons of 0.55 molar NaTPB solution to Tank 48H, asproposed for the Process Verification Testing Phase 1 (PVT-1),will achieve this level of decontamination. Neither the source ofthe NaTPB (Tank 49H or vendor supplied solution) nor the presence“of organic decomposition products currently in Tank 48H affect thedecontamination.

Excess sodium tetraphenylborate in Tank 48H is susceptible todecomposition and the rate is strongly influenced by temperature.Limiting Tank 48H to 40 ‘C slows the rate by an order of magnituderelative to 50 “C. At the slow decomposition rates measured at40 “C and with an initial soluble NaTPB concentration of 100 mg/L(obtained by addition of 175 gallons of 0.55 molar NaTPBsolution) , the decontamination of the salt solution is maintainedfor ten days or longer. At the fast rates measured at 50 “C, theexcess NaTPB decomposes in less than two days.

After the excess NaTPB decomposes, the soluble CS–137 levelincreases. As measured in laboratory tests, the initial rate ofincrease can be very rapid (>100 nCi/mL/day) , but slows within afew days. This phenomena was not observed in Tank 48H, where aconstant rate of increase (1.4 nCi/mL/day) has been measured forover nine months. The CS–137 increase is due to decomposition ofa small amount potassium and cesium tetraphenylborate solids (KTPBand CSTPB) . The largest increases in soluble CS–137 measured inlaboratory experiments correspond to decomposition of 0.05 to 0.5%of the solids.

Further work is required to fully understand the decomposition ofthe excess NaTPB. Some test results imply that rapid decomposi–tion occurs at temperatures lower than 50 “c. Also, the factorsaffecting the decomposition rate of the solids are not known.Suggestions for further studies in these areas are presented.

Introduction

The In-Tank Precipitation (ITP) process started radioactiveoperations in Tank 48H in August 1995. Three months later, theexcess soditi tetraphenylborate (NaTPB) in the tank decomposed at arate more rapid than expected from prior experience and testing.1The decomposition has necessitated deferring full production in ITPuntil additional Process Verification Tests (PVT-1, PVT-2, etc.)complete. 2 These tests include laboratory experiments with highlevel waste slurries in~the SRTC Shielded Cells Facility. Thepurpose of the Shielded Cells testing is to demonstrate the changesthat occur from chemical additions to the slurry in Tank 48H. Inparticular, the tests should provide information on CS-137decontamination, the rate of decomposition of NaTPB, the rate of


increase in CS–137 following loss of NaTPB, and the rate ofproduction of benzene and other decomposition products.

The PVT plan changed several times during its development, butalways included two phases. The first phase (PVT-1) adds a smallamount of NaTPB to Tank 48H to demonstrate the precipitation ofsoluble CS–137 and to measure the rate at which the excess NaTPBdecomposes. The original plan was to add Tank 49H salt solution,which contains residual NaTPB from the 1983 full–scaledemonstration. However, due to concerns about the transfer routefrom Tank 49H to Tank 48H, the plan changed to add NaTPB from drumsof solution prepared by Honey Oak Chemicals. The second phase(PVT-2) adds fresh waste, dilution water, Tank 49H salt solution,and additional NaTPB solution from Honey Oak Chemicals.

The results of the demonstration tests to support PVT-1 arereported below. Decomposition of tetraphenylborate and increasesin soluble CS–137 were observed and several of the factorssuspected of affecting rates have been examined. The results todate do not provide an adequate understanding of the phenomena andfurther work is suggested.

Identification of Experiments

The experiments completed in support of this program have beennumbered to simplify identifying them in the following discussions.Table I provides this numbering system with a brief description ofthe major features of each experiment. This numbering system isused consistently in all of the tables in this report and in otherreports referring to these results.4 Chronologically, Experiments#1 through #4 were performed in the sequence in which they are‘numbered. Experiments #5 and #6,” although perfo~ed earlier than#1-#4, are included at the end of the list because they used quitedifferent protocols and the results are not directly comparable toExperiments #l-4. The results, however, have been widely discussedand are included here for completeness.

Precipitation of Cs-137

Decontamination of the supernate in Tank 48H slurries has beendemonstrated in several experiments. The results support thefollowing conclusions.

●

●

●

Precipitation of CS-137 occurs within 2-4 hours of addingexcess NaTPB.

Soluble CS-137 is reduced to less than 12,nCi/mL with excessTPB- concentrations less than 150 mg/L.

Neither the source””of the NaTPB nor the organic decompositionproducts currently found in Tank 48H significantly affectdecontamination.

. TABLE 1. Summary of Experiments

.

w!: Experiment __________

- .. . ... . .. .._._.._.i=.

:>~/::F! $: E %::E:gF-sGResult ._.___..,_____ -_-L----- —.-... —- P

v. -=-jg~~~-w,%-e. .

sol,,,ve$s~!.~~.....w....~.-..

..,..-.---.-,..—..—___._._...__ _.-.______. _________. ----. —- ..—.. -.__ _ .____....._ .,,,__...

,- Decontamination Test _ CS-137 reprecipltated

..—--- ——— —— .-— ._. _- ,.,TPEQ&omposition.,TS+!

——.——— .— .._-- ..— ——rapid )0SS of TPB. (24 hr)

,yithlk49HNaTPB . . . . . . Cs.137 jumped to 534 nC!JmL.—

-.. ..——— —__(.- TPB. Decomposition Test

,at Low W!. Y.. SOM!

*---”b:+~l’+*’-+*’*R+~::d’-:’d

.. . ,—____ —.--.-——J---— —.————New Batch Simulallon Test

~O.?:_E:c*,---...p,K~,FI[!:H,A?zH,A?z::00 ~, -y-.-+l-.- . . . Z?

–- .. . . ...2.-. . ..-. -+.:06;-- ~o-ii- --- I .-.—... —..-.—.L_- -.. T________ .—— .. . . . __

with Tk 25F and Tk 26F Waste Soltdlons

Jearty experiment)+-.— ------- .— . . . . _ ..__

—

* The three sources of sodium tetraphenylborate are:Tank’49H: salt solution from Tank 49H which ~ontaln~

residual NaTPB from the 1983 full scale In-TankPrecipitation demonstration.

Al?F/Aq: Representative composite sample from the truckloads. of,AFF/Aquafine NaTPB solutions added to Tank 48H

during September 1995,HOC : Solution prepared by Honey Oak Chemicals from AFF

NaTPB that had been spray dried by Aquafine. Thisbatch was identified as the probable source of NaTPBfor the PVT-1 plant test,

** poly = polyethylene; ss = stainless steel; cs . carbon steel

Olul● u-lo

PPw.:U3o-l

‘ lPB = phenylboronic acid, (CCHS)B(OH)22PB = diphenylborinic acid (C6H5)2BOH3PB = triphenylboron (C6H5)3B

“ NA = not available

‘“ Corrected for dilution.

,.

~ WSRC-TR-96-0190Page 5 of 35September 6, 1996

TABLE

Emt .#

1

2

3A

3B

4A

4B

6

11. Results of Preci,pi.tation of CS-137

Tank 48HSampleDate

5/8/96

6/2/96& 5/8/96

6/28/96

6/28/96

7/96

7/96

1/21/96

NaTPBSourcea

Tk 49H

Tk 49H

Tk 49H

AFF

HOC

HOC

Tk 49H& AFF

FinalNaTPB

JJIKlfU

66134

1260

128

93

86

94

103

10,000’

Cs-137(nCi/mL)b CommentsInitial Final

280 1.9280 1.1280 0.4

280 3.0

300 2.6

70 3.8

335 11.7

335 5-0

3X105 4.8

Simulated saltsolution & watezadded.

Salt solutionfrom Tk 25F &Tk 26F and watadded

a Tank 49H solution was a composite of several dip samples taken4/96 and the TPB- concentration was 0.023 M. AFF solution was 0.55MNaTPB and was the same material that was added to Tank 48H inAugust 1995. HOC (Honey Oak Chemicals) solution was 0.59 M lVaTPBintended for use in the PVT-1 test. These solutions are describedfurther in Appendix A.b Note that the values listed are in units of nCi/mL. If expressedas nCi/g (as is usual when referring to the Saltstone procesSlimits), the values would be 10-20% lower.c Includes insoluble NaTPB.

Table II lists the results from several experiments and furtherdetails are given in Appendix A. In all of the experiments, CheNaTPB was added to ‘Tank 48H slurry or a mixture of Tank 48H slurrywith other salt solutions, stirred for 2 to 4 hours at ambienttemperature, and filtered through a nominal 0.45 micron pore sizefilter.

In these experiments, the final CS–137 concentration varied .in the”range 0.4 to 12 nCi/mL. Variations in this range are unimportantto the process since the acceptable limit. is much higher. Thevariations are probably due to differences in slurry composition,excess NaTPB, temperature, mixing, length of time before sampling,and small random errors in sampling and analysis.

. . ,.

wSRC-TR-96-0190Page 6 of 35September 6, 1996

The effect of excess NaTPB was examined in the first experiment(Table II), where,incremental amounts of Tank 49H salt solutionwere added to Tank 48H slurry to determine the amount required toprecipitate the potassium and CS-137. As expected, increasing theexcess soluble tetraphenylborate decreases the soluble CS–137.Adequate decontamination was achieved with as little as66 mg/L TPB- in solution. However, for reasons cited above, theexact concentration of soluble CS–,137 is variable (0.4 to11.7 nCi/mL) when the soluble TPB- is in the range 66 to 134 mg/L.

Efficient .decontamination was achieved using tetraphenylborate fromeither Tank 49H, AFF/Aquafine, or Honey Oak Chemicals. Also, theorganic decomposition products currently” in Tank 48H do not preventacceptable decontamination provided excess NaTPB is present. Thelevels of phenol and phenylboronic acid [(CGH~)B(OH)z) or lPB] areshown in Table I. Phenol varied between 250 and 1579 mg/L; lPBvaried between 69 and 922 mg/L.

Decomposition of Soluble Tetraphenylborate

The rate of decomposition of NaTPB in Tank 48H slurry samples hasbeen measured in several experiments in the SRTC Shielded Cells.The

●

●

●

results show the following.

The rate of the decomposition reaction increases significantlywith temperature between 40 and’ 50 “C. In general, the rate ofdecomposition is slow at 40 ‘C (O-5 mg/L/day) and fast at 50 “C(34 to 63 mg/L/day).

There appears to be a correlation. between the rate of loss ofTPB- and the weight percentage of Tank 48H solids present in theslurry. This result implies that the solids either contain acatalyst (for example, heavy metals in the sludge portion ofthe solids), or provide a medium for the reaction (for example,the surface area of the KTPB particles) .

The following factors do not show a correlation to the rate ofdecomposition:

– concentrations of decomposition products (lPB andpheno 1)

- the source of NaTPB,– the materials of construction of the reaction vessels,– the date the Tank 48H slurry was taken, or– the concentration of the salt solution.

The experimental conditions and results are given in Table I. Formost emeriments, the soluble CS-137, NaTPB, lPB, and phenolconcentrations were mea~.ured over awas held at temperature. Graphs ofdescriptions, and data are given in

period of time whiie the slurrythese concentrations, detailedAppendix A.

.,

WSRC–TR-96-0190Page 7 of 35September 6, 1996

The decomposition of excess Na.TPB can beTPB- concentration in filtrate samples.amounts of TPBJ are present in solutionCS-137 concentration remains low (0.1 to

followed by measuring theAs long as measurable(>50 mg/L), the soluble12 nCi/mL). The

concentration of soluble CS-137 should increase as the TPB-concentration decreases. However, due to reasons cited in thediscussion of decontamination, the trend is not always discernibleabove the random variations in the data. Nevertheless, the datawithin some experiments does show a slight upward trend in solubleCS–137 as the TPB- concentrations decreases (for instance, see thedata from Experiment #4 in Appendix A) .

When the decomposition of soluble TPB- is complete, then the soluble ‘“”CS–137 concentration in filtrate increases. In Tank 48H, the rateof increase has been constant at approximately 1.4 nCi/mL per daysince early December 1995.1 Since an increase in soluble CS-I.37indicates decomposition of the solid tetraphenylborate compounds inthe slurry, and since the solids are largely potassiumtetraphenylborate, the increase in CS–137 is accompanied by anincrease in soluble potassium ion. This correlation has beenobserved in Tank 48H. The organic decomposition products (lPB,phenol, and benzene) may also indicate the extent of reaction ofTPB- , although they are not as sensitive a measure as the changes inTPB- and CS-137. This is especially true of Tank 48H slurries thatalready have large amounts of the other organics present. A smallchange, in TPB- will not produce enough lPB or phenol to create adetectable change in their concentrations.

The rate of decomposition of TPB- can be estimated from the resultsof eight experiments (#2, #3D, #3E, #4A, #4B, #4C, #4D and #5), butnot from three that appeared stable (#3A, #3B, and #.6). Theinitial rates of loss TPB- are listed in Table I. Note that this isan approximate method of comparing the results from differentexperiments. A more rigorous analysis of the data, using rateconstants for the reactions, appears in a separate report.4However, the initial rate of loss is used for qualitativecomparisons in the following discussions.

Two experiments (Table’1, Expt.#2 and #5) present problems inestimating the initial rateof TPB- decomposition. In Experiment#2, the TPB-’concentration was 74 mg/L after 1 day, the solubleCS-137 concentration was 534 nCi/mL, and the soluble potassium ionconcentration was 7 mg/L. The presence of all three in solution iscontradictory since all other work indicates that ~he CS–137 andpotassium should precipitate if soluble TPB- is present. It islikely that there was an error in sampling or analysis. If the TPB-analysis is correct, then the rate of loss of TPB- was 54 mg/L/day.If the CS-137 and K+ values are correct, then the TPB- concentrationmust have been lower th~n measured and the race of loss of TPB- wasgreater than 54 mg/L. Because of this uncertainty, the Table Ientry for the decomposition rate in Experiment #2 is listed as>54 mg/L/day. In Experiment #5, the available data yields anextremely high estimate of the rate of decomposition. Enough NaTPB

. .


was added to the slurry to produce an excess of 17,000 mg/L.After mixing for 4 hours at ambient cell temperature (27 “C),. a e

diluted sample was taken. The sample contained very little NaTPB(134 mg/L) and indicates a decomposition rate of 100,000 mg/L/day.This rate is 2,000 times larger than observed in any of the otherexperiments reported here. Unfortunately, the sample was notanalyzed until 37 days later- Thus , the excess NaTPB may havedecomposed during this time period. The first sample after heatingto 50 ‘C was taken at 16 days, but problems with the analysisresulted in no measurement of the TPB- concentration- However, thehigh soluble CS–137 concentration indicates that little or no TPB-was present at this time. The rate derived assuming not TPB-remained after 16 days is 700 mg/L/day or about 15 times fasterthan measured in other experiments. The dilution of the sampleduring its preparation (see Appendix A for details) alsocontributes to the uncertainty about the CS-137 concentrations-Because of these uncertainties, the Table I entry for thedecomposition rate in Experiment #5 is listed as >700 mg/L/day.Because of the problems and inconsistencies in the data from thesetwo experiments, the results should be used with caution.

Effect of Temperature

The rate of the decomposition reaction increases significantly withtemperature between 40 and 50 ‘C. In general, the rate ofdecomposition is slow at 40 ‘C (O-5 mg/L/day) and fast at 50 ‘C(34 to 63 mg/L/day). Experiments #2 and #5 suggest that the rate a —

may be significantly faster. The temperature effect is clearlyseen by comparing results from Experiment 4A, 4B, 4C, and 4D(Figure 1). Based on this data, the energy of activation for the

FIGURE 1. Effect of Temperature on theTPB- Decomposition Rate

3oa

200

100

0

Expt.#3E

Expt.#3Bd

J

50 “c

ti~

40 “cExpt.#3D

?Expt.#3A

, ,

300

zzE 200

c0=m.

z.:

c

E 100

CA0.1-

n0 10 20 E-’ 30 0

\

Expt.#4C

d

,

Expt.#4B \

J 50 “c

%\~

40 “c

t

ExPt.#4D

Expt.#4A

10 2“0 30

Elapsed Time (days)Elapsed Time (days)


reaction is 160 to 215 kJ/mole. This is consistent with previousmeasurements on similar systems.1

The inconsistency of Experiment #2 (higher rate at a lowertemperature) may have been due to poor temperature control. TheTPB- decomposed largely during the first two days of the experimentwhen temperature readings were higher than the average. Over theentire experiment, the temperature readings averaged 39 “C, butvaried between 32 and 47 “C. Some of this range was due to rapidchanges of the air temperature in the oven from the on/off cyclingof the heating element (see discussion in Appendix A) . However,this cycling does not account for the entire range. Thetemperatures recorded during the first two days of the experimentwere 45 and 47 ‘C, much higher than the average temperature. Theactual temperature of the slurry was at least 42 ‘C and may havebeen several degrees higher. Thus , the high decomposition ratemeasured in this experiment may be partially due to the high oventemperature during the first two days. A

Effect of Weigh~ Percen~age Solids

There appears to be a correlation between the rate of loss of TPB-and the weight percentage of Tank 48H solids present in the slurry.The decomposition rates from Experiment #4 (at 4 wt % solids) areconsistently faster than corresponding results from Experiment 3(at 0.6 wt % solids). Also, the two anomolous experiments (#2 and#5) both contained relatively high amounts of solids (Expt.#2,3.7 Wt %; Expt.#5, 5.1 wt %). This result implies that the solidseither contain a catalyst (for example, heavy metals in the sludgeportion of the solids), or provide a medium for the reaction (forexample, the surface area of the KTPB particles) .

The total solids listed in Table I includes both organic solids(KTPB and CSTPB), and inorganic solids (monosodium titanate andsludge) . The inorganic solids were measured after dissolving thetetraphenylborate solids in acetonitrile. The inorganic solidswere dissolved in.aqua regia and analyzed to determine theelemental composition. The results are listed in Table 111. Thepresence of boron suggests that some KTPB was probably left in theinorganic solids due to incomplete washing. The weight percentageof inorganic solids reported in Table I are corrected for thepresence of KTPB assuming that the boron due to KTPB. The ratio ofinorganic to total solids is relatively constant in all of theslurries (0.13*.03), as is the ratio of monosodium titanate tosludge, shown by the ratio of Ti/Fe (9fl) . This is consistent withprevious studies that found that monosodium titanate and sludgesolids do not significantly separate from KTPB solids by gravitysettling.5 Since these ratios were constant, the separatecontribution of inorganic solids or organic solids to differencesin the rate of decompos~tion of TPB- cannot be determined from thisdata set.

WSRC-TR-96-0190Page 10 of 35September 6, 1996—

TABLE 11-1. Composi.ti.on of Inorganic Solids

.,. . ,

Element

AlBBaCaCdcoCrCuFeMgMnMoNaNiPPbSiSnSr ~TivZnZr

CompositionExDt#2

3.1, 1.9.76, 1.108, .05:46, .29.01, .01.05, .03.31, .20.06, .04

2.5, 1.6.56, .36.24, .15.01, 01

6.6, 4:5.12, .12.16, .08.15, .10

2.3, 1.2.03, .02.02, .01

22.5, 14.2.03, .02.07, .07.03, .02

(wt % in i.norgani.c solids)ExDt .#3 ExDt .#4

3.1.67.08.57.04——

.30

.062.9.57.25——

4.8.27.20——

1.7——

‘.0223.3

——

.11——

2.8, 1.41.3, 1.5.14, .05.54, .25.01, .00.07, .03.26, .15.07, .03

1.7, .90.40, .24.17, .1003, .01

5:3, 3.0.15, .06.24, .08.29, .11

1.7, .87.06, .02.02, .01

15.0, 9.4.05, .02.11, .04 e

.06, .02

The elements found in the analysis of the sludge solids and theirrelative concentrations are similar to previously reported results.1

Effect of Decomposition Products

The concentrations of decomposition products (lPB and phenol) donot show a correlation with the rate of decomposition, althoughfurther study is warranted. In the experiments that showed rapidloss of TPB- (#2, #3D,. #3E, #4C, #4D, and #5), the concentration oflPB varied between 111 and 1980 mg/L and the concentration ofphenol varied between 1073 and 1579 mg/L. These values encompassalmost the entire range found for both compounds. The other majorintermediates (3PB and 2PB) were not measured because an analyticalmethod was not available at SRTC. Their concentrations areexpected to be linked to lPB, which suggests that there is nocorrelation between them and the decomposition rate. This issupported by the similarity of the TPB- decomposition rate inExperiments #4C (no intermediates added) and #4D (with 3PB and 2PBadded) . *..

o


Effect of NaTPB Source, Vessel Material, Tank 48H samplingDate, and Salt Concentration

There does not appear to be any correlation between the reactionrate and the source of NaTPB, the materials of construction of thereaction vessels, the date the Tank 48H slurry was taken, or theconcentration of the salt solution. At various times, these wereproposed as possible causes for the high rate of decomposition inExperiment #2. For example, high rates of decomposition have beenobserved with all three sources of NaTPB (Tank 49H, AFF/Aquafine,Honey Oak), in reaction vessels from all three materials ofconstruction (polyethylene, stainless steel, and carbon steel] , inTank 48H samples from 12/95 and from 7/96, and from the entirerange of sodium ion concentrations (3.5 to 5.1 molar) .

Effect of Batch Dilution

Tests #3B and #6 were designed to examine the effect of the currentTank 48H slurry heel on the chemistry of a subsequent batch ofwaste. In both cases, decontamination was rapid and’the NaTPBremained stable for an extended period of time. For example, inTest #6, the majority of the excess NaTPB was still present aftersix weeks at 50 “C. The improved stability may be due to dilutionof the active catalyst.

Decomposition of Insoluble Tet.raphenylborates

During Experiment #2, a sudden increase in the soluble CS–137concentration was observed (Figure 2) . Following the jump, theCS–137 concentration continued to increase, but at a much slowerrate. A corresponding increase in soluble K+ ion was also observed.The jump to 550 nCi/mL of soluble cesifi is equivalent to thedecomposition of 0.10 wt % of the solids present, based on valuesof 4X105 Ci and 200,000 gallons of slurry in Tank 48H. If thechange in potassium ion concentration is used to make the calcula-tion’ (using 3.2 wt % KTPB in a slurry of density 1.14 g/mL), then asimilar decomposition value of 0.17 wt % is obtained. The rate ofincrease in soluble CS-137 following the jump is 12 nCi/mL/day.This value is about eight. times larger than the current rate ofincrease in the Tank 48H, but the difference may be due largely tothe differences in temperature between the experiment and Tank 48H(less than 35 “C since December 1995).

“In Experiment #5, the magnitude of the jump in soluble CS-137 andits subsequent rate of increase are not clearly evident due to thelarge and apparently random scatter in the CS-137 measurements.However, the extent of decomposition can be determined if thefollowing are assumed or calculated:

(1) dilution durin~” sampling did not dissolve any CS-137,

(2) total decomposition of excess NaTPB yields1170 mg/L boron in solution, and

.

wSRC-TR-96-0190 \Paae 12 of 35Se;tember 6,

FIGURE 2.

1996

Increases in Soluble CS-137 FollowingDecomposition of Tetraphenylborate

800-

Expt.#2

600-

400-

200 -

0

0 10 20

Elapsed Time (dsys)

)

(3) the boron measurement (relative to 1170 mg/L) is usedto calculate the dilution of the sample.

On this basis, the extent of the solids decomposition in Expt.#5was 0.5% after 16 days when the first CS–137 measurement was made.

In Experiment #4D, a jumP in CS–137 was observed (Figure 2) .However, since the slurry was entirely consumed in taking thesample showing the jump, there was no corroborating evidence thatthe jump was completed (i.e, would not have been higher in asubsequent sample) . In addition; the last sample was too small toobtain confirmation by K+ analysis. However, assuming the jump wascomplete when the last sample was taken, then the change in the Cs-137 concentration corresponds to a 0.04% decomposition.of thesolids. >

In the other experiments, this phenomenon (jump in soluble CS–137followed by slow increase) was not observed, presumably because theexcess TPB- was never completely consumed. It may have beenobserved if the experiments had continued until all the TPB- wasdecomposed.

Decomposition Rates Expected in Tank 48H During PVT-1

Eased on the preponderance of data from the experiments describedabove, the rate of loss of TPB- ion in Tank 48H is expected to be5 mg/L/hr or less if th~.tank temperature is maintained below40 Oc- This is based on the resultsof Ex~eriments 4A and 4B whichmost closely’ imitate the planned addition of sodiuri tetraphenyl–borate in PVT-1. The rate of decomposition is proportional to theTPB- concentration,4 so a faster rate would be found if the initial


TPB- concentration is higher (i.e, if PVT–1 uses more than 200gallons of NaTPB solution) . The results from Experiments #3A ~d#3B support a decomposition rate of less than 5 mg/L/day. However,the results from Experiments #2 and #5 suggest that a factor notadequately controlled in these experiments could affect the rateand cause the excess NaTPB to decompose at a rate more than 10times as fast.

Solids degradation and release of CS-137 to solution is not likelyto occur during PVT-1 as long as the rate of decomposition of theexcess TPB- is slow. CS-137 release did not occur in Tank 48Hfollowing the decomposition during November and December 1995.However, even if it does occur, then the extent of the reaction, asindicated by the results of Experiments #2, #4D, and #5, is only

0.05 to 0.5 % of the solids in the tank. Since there areapproximately 22,000 kg of tetraphenylborate solids in Tank 48H,the decomposition would produce 10 to 100 kg of benzene.

Effect of Nitrogen Inerting

The reaction atmosphere has been shown to influence at least twoaspects of the NaTPB decomposition reaction sequence. In air, thereaction exhibits an induction periodl and, when coupled with a highhydroxide salt solution medium, favors production of phenol ratherthan benzene.s The presence of pure nitrogen results in no delay inthe onset of the reaction and favors production of benzene relativeto phenol.1 The length of the induction period observed in air”depends upon reaction temperature. Induction periods as short a=100 hours have been observed in reactions at 70 “C. An inductionperiod of 450 hours was observed in a reaction at 40 “C. Oneaspect of the reaction that is not influenced by reaction’at~osphere is the rate of TPB- decomposition.period is ignored and reaction start time isthe end of the induction period, the rate ofis similar to (or even slightly faster than)decomposition in nitrogen.1

if the inductionset to coincide withdecomposition in airthe rate of

After Experiment #2, the ability to conduct tests under an inertatmosphere in the Shielded Cells became available. The were manyreasons for selecting air rather than 5 vol % o~gen (in nitrogen)or pure nitrogen as the reaction atmosphere in the remainingexperiments. First, the reaction conditions and products are morestable. With air, leakage through the septa on the reaction vessel(after frequent sampling) would not produce a significant change inthe oxygen concentration in the vessel. If a 5 vol % o~gen (innitrogen) or pure nitrogen atmosphere were used, air leakage wouldproduce a significant change in the oxygen concentration within thereaction vessel. Second, use of air coupled with the highhydroxide concentration=.present in the test solution should producephenol as the primary decomposition product rather than benzene.Benzene is volatile and difficult to accurately measure inreactions in the Shielded Cells. However, phenol is non–volatileand much more accurately measured in reactions conducted in the

.““.,


Shielded Cells. Third, all previous Shielded Cells tests,including those that decomposed, were conducted using an airatmosphere. If the reaction atmosphere were not kept the same,comparisons between the new tests and the past tests would bedifficult to perform. Fourth, no data was available on reactionbehavior in 5-V01 % oxygen (in nitrogen) . From this standpoint,expectations of the reaction behavior would be difficult toaccurately predict and a reaction with this atmosphere would bemore difficult to analyze. Lastly, ignoring the induction period,reaction in air is more conservative since the rate ofdecomposition in air is a little faster than-the rate ofdecomposition in nitrogen.

Possible Mechanisms for the Decomposition ofTetraphenylborate Solids and Suggestions for Further Work

Several mechanisms suggested for the decomposition of the insolubletetraphenylborate solids are discussed below.’ Many of these havecome from a review panel composed of Robert J. Hanrahan, R. BruceKing, E. J. Lahoda, George W. Parshall, and R. A. Smiley. Testingto investigate the factors affecting the solids decomposition willbe included in the ITP chemistry technical plan.

The increase in soluble CS–137 may be caused by an equilibriumshift due to formation of a cesium-organo ,compound. This does notseem likely since cesium ion in aqueous solution shows littletendency to form coordinate compounds. This can be easily exploredby CSTPB volubility measurements in the presence of the organicdecomposition compounds.

Possibly, 2PB reacts with KTPB/CsTPB solids via a disputationreaction with the following stoichiometry:

(C,H,),B-+ (C,H,),BOH -—~ 2(CGH~)JB + OH-

The reverse reaction has been’published as the basis for thesynthesis of tetraphenylborate. The product (two moles of 3PB)could decompose providing more 2PB for the reaction withtetraphenylborate. This mechanism could be easily te=ted byadditional experiments with intermediate compounds.

Inorganic solids may catalyze the decomposition of KTPB and CSTPB,as suggested by the faster rates at the higher solidsconcentration. This reaction would very likely be mass transferlimited since solid-solid reactions are typically slow. Thismechanism can be tested by measuring the effect of sludge solids onthe reaction rate.

The increase in CS-137 may be due to decomposition of selectedsolids, in particular, very fine particles with high surface tovolume ratio. This could be studied by comparing the decompositionrates of freshly precipitated solids to those for aged or digestedsolids .

,

WSRC-TR-96-0190Page 15 of’ 35September 6, 1996

The slowest rates of solids decomposition (i.e.,may be due to catalyzed or thermal decomposition(from dissolution of the KTPB), or it may be due

the Tank 48H rate)of soluble TPB-to radiolvtic

degradation of the solids. Experiments ~sing CO–60 gamma ~adiationcan determine the contribution of the radiolytic mechanism.

Conclusion

Addition of as little as 0.0003 molar (100 mg/L) excess NaTPB tothe slurry in Tank 48H is sufficient to reduce CS-137concentrations below 10 nCi/g within a few hours. Thisradioactivity level is well below the current and proposed limitsin the ITP process requirements. Efficient decontamination wasachieved using tetraphenylborate from either Tank 49H,,@?F/Aquafine; or Honey Oak Chemicals. There is no evidence thatorganic decomposition products in Tank 48H prevents acceptabledecontamination as long as excess NaTPB is present. However, theexcess NaTPB will be at risk of decomposing. The rate of thedecomposition reaction increases sicmificantly with temperaturebetwe~n 40slow at 40mg/L/day) .the excesskept belowrates, butdecomposes

and 50 ‘C. In general, ~he rate o; decomposition is“C (O-5 mg/L/day) and fast at 50 ‘C (34 to 63The majority of the small scale tests indicate that

NaTPB will degrade slowly if the tank temperature is40 “c. TWO tests have shown faster decompositionthe results of these tests are suspect. If the NaTPBra~idlv, laboratory tests indicate that the-.

concentration of soluble CS–137 may increase to levels greaterthan they were prior to the precipitation. The extent of thisdecomposition is small, and has not exceeded 0.5 % of the solids.


References *

1. D. D. Walker, M. J. Barnes, C. L. Crawford, R. F. Swingle, R.A. Peterson, M. S. Hay, and S. D. Fink, “Decomposition ofTetraphenylborate in Tank 48H (U),” WSRC-TR-0113, Rev.0, May 10,1996.

2. 0. Cardona-Quiles, ‘\In–Tank precipitation Plan for processVerification Test,” HLW-ITP-960247, Rev.0, draft.

3. D.A. Pervis, “Review of Revisions to ITP PR for WSRC-TR-96-0136 (U),” memorandum to A. W. Wiggins, et al, dated August 29,1996. Westinghouse Savannah River Company, High Level WasteManagement Division, “Process Requirements 241-82H Control Room(u),“ wSRC-IM-91-63, Rev.13, June 1996, Section 3.1.3.2.

4. R. A. Peterson and R. S. Swingle, “Prediction.of Tank 48H andTank 50H Benzene Concentrations During Process VerificationTesting Phase I (U),” wSRC-TR-96–0257, August 17, 1996.

5. L. L. Kilpatrick, “Composition of Washed and Unwashed In–TankPrecipitate (ITP) Solids (U),” WSRC-RP-96-7, Rev.0, July 16, 1996.

6. M. J. Barnes, unpublished results, see Laboratory Notebook#WSRC-NB-95-184 .

@

.

“.

,.

wSRC-TR-96-0190Page 17 of 35Se~tember 6, 1996

APPENDIX AExperimental Methods

All experimental results are ,reco.rded in the following laboratorynotebooks :

wSRC-NB-95-23 (D. D. Walker)wSRC-NB-96-613 (D. D. Walker)wSRC-NB-95-82 (C. A. Nash)

Analyses

Benzene analyses were performed by gas chromatography bypersonnel within Interim Waste Technology using Procedure IWT–OP-005, Manual L12.1. The sample preparation method for radioactivesamples in the Shielded Cells has been described previously.1

The solids content of several slurries were measured in theShielded Cells by the following procedure:

a.

b.

e.

A portion of slurry (5–10 g) was weighed into a 30 mLsintered glass fritted filter (“Fine” porosity) .The salt solution was removed by filtration and the sol-idswere washed with three 10 mL portions of water.The washed solids were dried at 100 ‘C to constant weight.The dry solids were washed with three 15 mL portions ofacetonitrile to dissolve the tetraphenylborate solids.The inorganic residue was dried to constant weight at—100 “c. -

The inorganic residue was analyzed by treating the entire filterin aqua regia (30mL) . The aqua regia was decanted to a 100–mLvolumetric flask. The filter was rinsed with water and the wateradded to the aqua regia, with final dilution to 100 mL. All ofthe solids appeared to dissolve by this procedure. The resultsof these analyses are listed in Table III. Based on the boronresults (and the ratio of boron to the other inorganic elements) ,it is apparent that the acetonitrile washes were not entirelyadequate to r~ove all of the KTPB. The values for weightpercentage of inorganic solids have been corrected for residualKTPB in the washed and dried inorganic residue assuming that allof the boron is due to KTPB. .

All other chemical analyses were provided by the SRTC AnalyticalDevelopment Section (ADS) . Samples submitted for anlaysis wereassigned computer tracking numbers (LIMS numbers) by ADS and thenumber is recorded in the laboratory notebook of the researcherthat submitted the samp}e. All results were obtainedby routinemethods.

*Tetraphenylborate is measured by ‘two methods. At highconcentrations (>0.01 molar) , the preferred method is ‘

. .


~otentiornetric titration with silver ion. At lower.concentrations it is measured by High Performance Liquid

.

Chromatography (HPLC) . Tetraphenylborate, phenylboronic acid,and phenol were measured by HPLC. Boron and transition metalswere measured by ICP–ES atomic emission spectroscopy. Potassiumwas measured by atomic absorption spectroscopy. Cs-137 wasmeasured by gamma ray spectroscopy using an intrinsic germaniumhigh-resolution spectrometer. Cormnon solution ions (nitrate,nitrite, sulfate, phosphate, fluoride, choloride, and oxalate)were measured by ion chromatography. Hydroxide, aluminate, andcarbonate were measured by wet chemical techniques usingacid/base titrations.

Sources of NaTPB

The following three sources of NaTPB were used in the experimentswith Tank 48H slurry.

Tank 49H

This solution was a composite of four VDS samples taken from Tank49H in April 1996 (Sample nunibers ITP-273, ITP-274, ITP-275, andITP–276) . For the decontamination and decomposition tests, thecritical component in this solution was tetraphenylborate ion.The following results were obtained on two of the VDS samples inthe composite:

a

Based onTank 49H

S%rmle ConcentrationTPB- Phenol PBA Biphenyl Terphenyl-@L ~ -@l@_ Q@Q J2MfliL

ITP-274 .024 407 <20 6 2ITP-275 .022 413 <20 5 2

analyses of! other recent samples, the composition ofsalt solution was:

Component Concentration(molar) #

Na’ 3.2NOl- 0.62NOz- 0.90OH- 0.17co32- 0.28so42- 0.033A102- 0.05Oxalate 0.008

w“Reference: M. J. Barnes, “Inadvertent Transfer of Tank 49H SaltSolution: Status Report 1 (U),: WSRC–TR-96–0246, Rev.O August 9,1996.

.

WSRC-TR-96-0190Page 19,0f 35September 6, 1996

*

a

e

Table A-I. CompositionSolutions

Component

NaTPB (molar)NaOH (molar)Phenol (mg/L)lPB (mg/L)

of AFF and Honey Oak NaTPB

ConcentrationAFF Hollev Oak

0.58 0.590.10 0.12

1500 2100610 480

AFF NaTPB Solution

This material was a composite of samples of the NaTPB solutionsadded to Tank 48H in September 1995. The concentrations of majorcomponents are listed in Table A–I and detailed analyses beendescribed previously.’

Honey Oak

This material was from a sample of NaTPB solution received fromHoney Oak Chemicals. It was prepared from AFF NaTPB that wasspray dried by Aquafine. This solution was prepared by HoneyOak Chemicals with the intention of sending it to SRS for use inthe ITP Process Verification Tests. The sample was identified as#D-1558, pulled from the Honey Oak storage tank on 7/16/96. Theconcentrations of major components are listed in Table A–I.

Temperature Control During Shielded Cells Tests

Because of the high radioactivity in the Tank 48H slurries usedin the following tests, the experiments were conducted in theSRTC Shielded Cells Facility. A drying oven was used to incubatethe slurries at either 40 or 50 *C. Temperatures within the ovenwere measured using stainless steel–encased bimetal temperaturesensing helix–type Ertco thermometers (Ever Ready Thermometer) .TWO thermometers were used, one with a stem length of 6 inchesand one of 12 inches. The accuracy of the thermometers at twotemperatures was checked prior to use against a mercury-in-glassthermometer traceable to NIST. Following use, the thermometerswere checked in the Shielded Cells using an ice/water bath andboiling water. Both before and after use the thermometers werefound accurate to within *2 ‘C.

During use, the oven air temperature was found to vary by *5 “Cas the heating element cycled. The cycle time was approximately30 minutes. However, when the thermometer was

.


TABLE A-II. Summary of

# ofExPt# Measurements Hi.qh2 13 473 A&B 6 463 D&E 51 564 A&B 67 454 C&D 21 545&6 51 52

Temperature Measurements

Temperature (“C)

Low Median32 4032 3836 4537 4048 5245 50

Average(ranqe)39 (*8)39 (*8)46 (*1O)40 (*5)52 (*4)50 (*5)

placed in water held in a polyethylene bottle or in one of thesteel vessels used in the experiments, the temperature changeduring a cycle was less than *2 ‘C.

It was also found that the oven temperature (the mid point in thecycle) did change during experiments, possibly due to inadvertentmovement of the control.dial. A summary of the temperaturemeasurements is given in Table A–II. For experiments #2, #3, #5,and #6 the temperature was measured in air, and in Experiment #4the temperature of a bottle of water was measured. In thefollowing descriptions of the experiments, the average and rangefare quoted.

Experiment #1: CS-137 Decontamination Test

The purpose of this experiment was to demonstrate that theTank 48H slurry could be decontaminated to a level acceptable forprocessing and to determine the amount of Tank 49H solutionrequired to achieve decontamination. For this experiment, acomposite sample of Tank 48H slurry (94 mL) was prepared from thefollowing three VDS samples taken on 5/7/96: ITP-289, ITP-290,and ITP-291. The decontamination test started on 5/22/96.

The composite,Tank 48H slurry was stirred in a small polyethylenebottle. Duplicate samples were taken for analysis before anyTank 49H solution was added. This initial slurry was’divided infour parts and portions of Tank 49H salt solution were added toeach part. The source of NaTPB was the composite solution fromTank 49H described above. The volume of Tank 49H solution wascalculated as the equivalent number of gallons added to the188,000 gallon inventory of slurry i.nTank 48H. The experimentat 390 gal/tank corresponds to the stoi.cliometric amount of NaTPBrequi,red to precipitate the K+. The experiment at 140,000gal/tank corresponds to transfer of the entire contents of Tank49H to Tank 48,H. The slurries were stirred for 2 hours atambient temperatu.res, then filtered through nitrocellulose

‘ disposable filter (0.45”micron nominal pore size). The filtrate’ ‘was removed from the Shielded Cell and analyzed the the SRTCAnalytical Development Sect,ion. The results are listed in e

,.


TABLE A-III. Results for Experiment#l+

Tk 49H Vol. CS-137 Final Concentrations (mg/L)(Cfal/tank) * (nCi,/mL) EL _TPB~ ~ PBA Phenol

o 269*5 4.1 64 488k5 761 11470 284*6 4.1 63 490*5 728 1152

390 114*2 3.5 68 484 658 10936000 1.9i.05 0.34 66 504 668 1140

12000 1.1*.3 0.30 134 480 650 1094140000 0.4&.02 0.20 1257 342 381 789

‘The experiment was completed on 5/22/96 and the HPLC analyses onfiltrate were completed by 5/24/96.*The volume ratios used in the experiment are calculated as theequivalent number of gallons of Tank 49H solution that would haveto be added to’188,000 gal of slurry in Tank 48H.

Table A-III. The analyses were completed within two days offiltering the solutions. Although a delay in analysis of thefiltrate samples< will not affect measurements of CS-137, K+, orB, slow decomposition of TPB- and t_he intermediate decompositioncompounds (3PB, 2PB, and lPB) could affect the amounts of TPB-,lPB, and phenol observed.

Experiment #2: TPB- Decomposition Test with Tk 49H NaTl?B

The purpose of this experiment was to determine the stability ofthe Tank 48H slurry after an NaTPB addition. The stability wasmonitored by measuring the rate of loss of TPB- and the rates ofappearance of decomposition products. This experiment was thefirst that clearly showed rapid decomposition of the TPB- and ajump in soluble Cs-137.

,’

For this experiment, the remainder(23 mL) of the Tank 48H slurrycomposite prepared for Experiment #1 was combined with thefollowing two samples taken from Tank 48H on 6/2/96: ITP-296(58 mL) and ITP-297 (63 mL). To this was added 4.6 mL of Tank49H solution (ratio: 6,000 gal Tk 49H/188,000 gal Tk 48H). Afterstirring for 2 hours at ambient temperature, a 30 mL portion wasfiltered (0.45 micron) and the filtrate removed from the cell fora separate benzene generation test (see below) . The remainder ofthe slurry (107 mL) was placed in a stainless steel reactionvessel (cylindrical, 4 cm diameter, 12 cm tall, 150 mL internalvolume) . A top plate containing three septa ports was bolted tothe cylindrical vessel using a Teflon washer as a seal. Thevessel was place in an oven at 39*8 “C-. Samples of slurry wereremoved from thevessel by inserting a stainless steel needlethrough silicone rubber septa in the ports on the lid. Thesamples (approximately ’@mL) were filtered and the filtrateanalyzed for CS–137 activity, potassium, TPB-, lPB, phenol, andtotal boron. Separate 1 mL portions were removed for benzene

-.


TABLE A-IV. Results for Experiment #2,TPB- Decomposition Test with Tk49H NaTPB ~

Elapsed Concentrations (mg/L)Time CS-137 g & TPB: PBA Phenol Benzene

(davs ) (nCi/mL)o 3*.I 472 0.2 128 461 12711 534*11 481 7.0 74 192 1417 29.56 551fll 461 <20 87 1738 39.8

17 685*11 492 10.1 <20 70 158224 6.326 836*11 497 11.2 <20 28 2704

tTest started on 6/13/96. HPLC analyses were run after thefollowing delays: Day O, same day; Day 1, 11 days; Day 6, 5days; Day 17, 2 days; Day 26, 2 days.

Figure A-1. Results from Experiment #2TPB- Decomposi.tion Test with Tk49H NaTPB

300 I

&:

100-

00 10 20 30

Elapsed Time (days)

0-300 10

1

0 10 20

Elapsed Time (dsys)

I

3CO0

.

2000-

T&g

Gc

:a. 100a -

a

.

0!o 10 20 30

Elapsed Time (days) Elapsed Time (days)

WSRC=TR-96-0190Page 23 of 35September 6, 1996

analyses. The results of these measurements are given in TableA–IV and graphs of the data are shown in Figure A-1. Many of thefiltrate samples were stored for several days and in some cases,weeks, before analysis.

The 30 mL portion of filtrate removed at the start of theexperiment was used in a separate test to measure the benzenegeneration rate in the filtrate. This sample was placed in aglass vessel at 50t3 ‘C. It was continuously stirred andventilated with air (10 mL/min) . The ventilation stream wassampled daily for benzene for 8 days. The benzene generationrate was 16*7 pg/L/hr.

At the end of Experiment #2, the weight percentage solids of theremaining slurry was measured in duplicate and the results were:

Total insoluble solids: 3.5, 3.9wt%Inorganic solids: 0.49, 0.89 wt %Inorganic solids (corrected) : 0.37, 0.57 wt %

The composition of the solids is listed in Table III.

Experiment #3: TPB- Decomposition Test with Low WeightPercentage Solids

Experiment #3A was a repeat of Experiment #1 to determine if theprevious observations were reproducible. The repeat experimentused a slurry sample that contained significantly fewer insolublesolids than Experiment #1. There were several other minordifferences between the two experiments. This experiment.indicated that the excess NaTPB was much more stable than foundin Experiment #1.

Experiment #3B, run simultaneously with #3A, was a scopingexperiment to determine .if rapid decomposition and increase insoluble CS–137 occurs in a new batch containing Tank 48H heel.

Experiment #3C was a control experiment run simultaneously with#3A and #3B. The purpose was to determine if any changes occurin a slurry to which no new NaTPB was added.

Experiments #3D and #3E were continuations at higher temperature(both) and with organic intermediates added (#3E) to determinethe effect on the decomposition. Temperature is shown to be amajor factor in faster decomposition rates.

For this experiment, a composite sample of Tank 48H slurry(232 mL) was prepared from the following three VDS samples takenon 6/28/96: ITP–,311, ITP–312, and ITP-313. The experimentstarted on 7/7/96. *.

The slurry was divided into three portions. Tank 49H solution.wasadded to one portion (Experiment #3A) . Simulated salt solution,

.“,,

.


dilution water, and AFF/Aquafinewere added to the second portionportion was used as a control todilution water (Experiment #3C).

NaTPB solution (Batch #AC-16)(Experiment #3B). The third

—

which was added a small amount ofA summary is shown in Table A-V.

As in Experiment #2, the slurries were prepared and stirred for2 hours at 24+5 ‘C. After stirring, initial samples were takenand the remainder of the slurries placed in three metalcontainers similar to the ones used in Experiment #2. Thevessels for Expt.#3A and #3C were stainless steel, and the vesselfor Expt.#3B was carbon steel. The metal vessels were placedinto an oven at 39A8 ‘C. Periodically, the vessels were removedfrom the oven and 6 mL samples taken via syringe. The sampleswere filtered through a 0.45 micron filter, and the filtrate wasanalyzed for CS–137, TPB-, phenol, and lPB. The results of theanalyses are listed in Table A–VI and graphs of the data areshown in Figure A–2. For these experiments, the HPLC analyseswere made within 24 hours of filtering.

After eight days, this part of the experiment was terminated.The remaining slurry in two of the vessels was used in acontinuation of the experiment at a higher temperature.Experiment #3B was not continued. Experiment #3A was continuedat 50 “C without any other changes (Experiment #3D) . Experiment#3c, the control, was adjusted by adding Tank 49H solution, andthe three intermediate decomposition compounds (phenylboronicacid, diphenylborinic acid ’anhydride, and triphenylboron sodiumhydroxide adduct) . Th”e expected concentrations in the new slurrywere: TPB- , 210 mg/L; 3PB, 220 mg/L; 2PB, 244 mg/L; and lPB,1100 mg/L. After stirring for 2 hours at 26*5 “C in apolyethylene bottle, the slurry was sampled and the remainderreturned to the steel vessel and placed in the oven at 46+10 “C(Experiment #3E). Both slurries (#3D and, #3E) were sampled after1, 2, and 3 days, at which time the experiment was terminated.

The samples were filtered through 0.45 micron filters beforeanalysis. The results of the analyses are listed in Table A-VII.

At the end of this experiment, the following weight percentagesolids measurements of the remaining slurry in Expt.#3D were ~obtained:

Total insoluble solids: 0.8 wt %Inorganic solids: 0.11 Wt %-Inorganic solids (corrected) : 0.09 wt %

The composition of the solids is listed in Table III.


TABLE A-V.Composition of Slurries Used in Experiment #3

Experiment : 3A 3B 3CRepeat #2 New Batch Control

Tk 48H composite (mL) 83.1 23.3 82.7Tk 49H solution (mL) 2.8 0 0AFF/Aquafine NaTPB (mL) o 5.% oWater (mL) 0’ 42.4 2.8Simulate salt sol’n (mL) O 28.7 0

Na+ (molar) 3.4 4.7 3.4

TABLE A-VI. Results for Experiments #3A, 3B, and 3C

Elapsed Concentrations (mg/L)Time CS-137 TPB- PBA Phenol _(davs) Z?312&# (nCi/mL)o 3A 2.6 57 152 1244

3B 3.8 40 69 4063C 296 <20 232 1405

1 3A 3.5 72 219 11943B 2.1 67 72 4013C 332 <20 198 1251

2 3A 3.1 107 252 13083B 1.6 107 35 4313C 281 <20 161 1184

3 3A 2.8 106 154 13853B 0.1 65 53 3993C 274 <20 158 1310

5 3A 2.8 68 110 14013B 0.4 131 48 4393C 300 <20 122 i250

8 3A 3.5 144 122 13333B 0.3 107 51 4213C 318 38 124 1352

TABLE A-VII. Results for Experiments #3D,and 3E

Time CS-137 Concentrations (mg/L)(davs) ~ (nCi/mL) TPB- PBA Phenol

o 3E 5.5 178 922 14421 3D 7.4 50 108 1316

3E 9:1 ——* 809 15212 3D 4.6 71 68 1498

3E 21.8 ——* 797 17563 3D 11.8 41 ‘ <20 1541

3E >.1 32 214 2057

*Because of the high concentrations of decomposition products,the TPB- peak in the HPLC analysis was not adequately resolved-

-..


Figure A-2. Results from Experiment #3TPB- Decomposition Test with Low WeightPercentage Solids

300

200

i--mg

A

E100

0

39*8 “c46f10 “C

Expt.#3B Expt.#3E

+4

A?

fl

Expl.#3A 7’Expt.#3D

,0 5 10 15

Elapsed Time (days)

10043I

800 Ii

600-\

Expt.#3E

\/

39*8 “c ~

400- \

Expt.#3A \

200- Expt.#3B \

/

4

●

0

0 , , ,

0 5 10 15

Elapsed Time (days)

40

30

I46t10 “C

i Expt.

20- Y

10- 39*8 -c

Expt.#3A

_;4~ Expt.#

oExpt.#38

o 5 1“o 15

Elapsed Time (days)

2000

k

39*8 “c

:

/

Expt.#3E

gExpt.#3A

zc ~pt#3D

2n. 1OQo

o~o 5 10 15

.Elapsed Time (days)

.————————————— _______———————————————————————————————————.

Experiment #4: TPB- Decomposition Test at High WeightPercentage Solids

Experiment #4 measured the effect of insoluble solids on thedecomposition rate. It#as run in duplicate (#4A and #4B) todetermine the reproducibility of the procedure. The insolublesolids content was similar to Experiment #2 and higher thanExperiment #3. *


Experiments #3D and #3E were continuations at higher(both) and with organic intermediates added (#3E) tothe effect on the decomposition.

temperaturedetermine

For this experiment, a composite sample of Tank 48H slurry(194 mL) was prepared from the following VDS samples.

ITP-320 (7/13/96) ITP-328 (7/17/96)ITP-321 (7/13/96) ITP-329 (7/17/96)ITP-322 (7/13/96) ITP-330 (7/17/96)ITP-323 (7/14/96) ITP-331 (7/17/96)ITP-324 (7/14/96)ITP-325 (7/14/96)

The total insoluble solids in these samples was low relative tothe slurry used in Experiment #2, so the solids were concentratedby decanting clear supernate from the top of the settled slurry.The original volume of approximately 675 mL was reduced to194 mL. The experiment using this composite slurry started on7/22/96.

A portion of the original slurry was used to measure the weightpercentage solids:

Total insoluble solids: 4.0, 4.lwt %Inorganic solids: 0.66, 1.34 Wt %Inorganic solids (corrected) : 0.38, 0.67 wt %

The “composition of the solids is listed in Table 111.

The slurry was divided into two portions (89 mL) . Honey OakChemicals NaTPB solution (0.12 mL) was added to each portion(Experiment #4A and 4B). As in previous experiments, theslurries were prepared and stirred for 2 hours at 27*5 “C inpolyethylene bottles. After stirring, initial samples were takenand the remainder of the slurries were placed in two new carbonsteel containers similar to the ones used in previousexperiments. Before use, the vessels had been rinsed-withacetone, then water, then soaked for 22 hours in 0.5 M NaOH, thenrinsed thoroughly with water again. After adding the slurries,the metal vessels were placed into an oven at 40+5 “C.Periodically, the vessels were removed from the oven and 6 mLsamples taken via syringe. The samples were filtered through a0.45 micron filter, and the filtrate analyzed for CS–137, TPB-,pheno 1, and lPB. The results of the analyses are listed in TableA-VIII and graphs of the data are shown in Figure A-3. For theseexperiments, the HPLC analyses were made within 24 hours offiltering.

r.

After four’teen days, this part of the experiment was terminated.The remaining .slurti in the two of vessels was used in acontinuation of the experiment at 50+5 ‘C. Experiment #4A

. ..

wSRC-TR-96-’0190Page 28 of 35September 6, 1996

TABLE A-VIII. Results for Experiments #4A and 4Bm

Elapsed Concentrations (mg/L)Time Expt# CS-137 TPB- PBA Phenol _(davs) ~ (nCi/mL)

o

1

2

4

7

10

14

4A4B4A4B4A4B “4A4B4A4B4A4B4A4B

11.75.09.79.2

13.017.523.316.217.412.720.020.432.124.2

9410377

10783

1137193657144612737

9310297

11511110898

10694

10288938066

11641181115011391131111910881143115011531154114111381244

TABLE A-IX. Results for Experiments #4C and 4D

ElapsedTime CS-137 Concentrations (mg/L)

(davs ) E2!Z2Q# (nCi/mL) TPB- PBA Phenol

o 4C 1.4 282 119 13994D 10.2 188 33.4 1579

1 4C 2.8 228 117 13064D 11.8 97 300 1458

2 4C 4.7 156 113 13984D 37 68 330 1484

5 4D 222 <20 441 2696

(25 fi) was continued at 52*4 ‘C after adding 0.060 mL of HoneyOak Chemicals NaTPB solution (Experiment #4C). Experiment #4B(37 mL), was adjusted by adding 0.060 fi of Honey Oak ChemicalsNaTPB solution and two intermediate decomposition compounds(diphenylborinic acid anhydride and triphenylborons odiumhydroxide adduct) . After stirring for 2 hours at 26f5 “C inpolyethylene bottles, the slurries were sampled and the remainderreturned to the steel vessels and placed in the oven at 50 “C.The slurries were sampled after 1, 2, and 5 days before theexperiment was terminated. There was insufficient slurry inExperiment #4A to obtain the 5 day sample. The samples werefiltered through 0.45 micron filters before analysis. Theresults of, theanalyses.are listed in Table A-IX and graphs ofthe data are shown in Figure A-3.

m.

WSRC-TR-96-0190Page 29 of 35September ’6, 1996

Figure A-3.

w

20Q

100

0

Results from Experiment #4, TPB-Decomposition Test with High WeightPercentage Solids

\

52+5 ‘C

\Expt.#4C

d

40*5 -c

\

Expt.#4B

%(

LExpt.#4D

d

tExpt.#4A

10 20 3

Elapsed Time (days)

500

52?4 ‘C

400

~_(”

K’Expt.#4D

300

200 40%5 ~c

Expt.#4B

100 ‘+_Expt.#4c

Expt.#4A+

o I,

0 I10 20 30

Elapsed Time (days)

r’

52*4 “C

/eExpt.#4D

: lCO 40*5 ~c

. Expt.#4A

+

-gJ., ~ExPt.#4c

oExpt.#4B

o 10 20 30

Elapsed Time (days)

40*5 “c

52?4 ‘c

/

~ Expt.#40

J

.

lmEExpt::v=:xpt”&;o 1’0 20

Elapsed Time (days)

.


Experiment #5: TPB- Decomposition Test with

The purpose of this experiment was to determine ifthe Tank 48H slurry would decompose. This was the

AFF/Aq NaTPB a

NaTPB added tofirst attem~t

to observe the decomposition reaction in a highly radioactive ‘slurry. The protocol for the test, particularly the samplingfrequency, the method of sample preparation (dilution followed byfiltration) , and the analytical methods used to follow thereaction (HPLC but not CS–137), were selected based on anexpectation of a slow response in the system. Consequently, theresults that were obtained were too sparse to adequatelydetermine when or how fast the reaction occurred.

For this experiment, a composite of the following two Tank 48HVDS slurry samples was made:

ITP-216 (12/18/95)ITP-217 (12/18/95)

The experiment started on 3/18/96. ,

A 10.0 ML sample of AFF/Aquafine NaTPB solution was dried at40.°C yielding 1.8 grams of solids. These solids were placed ina 125–ML polyethylene bottle and 104 ML of ‘the Tank 48H compositeadded. The slurry was stirred at 27t5 ‘C for four hours and thenan initial sample taken. The slurry was stored unstirred in anoven at 50t5 “C. Periodically, the bottle was removed from the aoven and a 5 mL sample taken’ for analysis.

The samples (5 g) were weighed into a glass beaker and 5 ML ofdilution water added to dilute the sodium ion concentration anddissolve the excess sodium tetraphenylborate. After stirring for15 minutes, the slurry was filtered. The beaker was washed withan additional 5 ML of water and the washwater passed through thefilter containing the slurry solids. The combined filtrate wasremoved from the Shielded Cells for analysis. The results ofthese analyses are listed in Table A–X. The HPLC analyses fromthis experiment were delayed several days or even weeks followingfiltration. Because of the washing of the solids andiconsequentdilution of the filtrate sample, gamma scans for soluble CS-137were not measured during this experiment. However, at the end ofthe experiment, an undiluted sample was taken and the dilutedsamples from earlier in the experiment were submitted for gammacounting. The insoluble solids collected in the filter were driedto constant weight. The results are also listed in Table A-X.

At the end of the experiment, it was found that the amount ofrinse water used to clean the beaker and wash the solids was notmeasured accurately after the first sample. Rinse water amountslarger than 5 ML were used, but the exact amounts were notmeasured or recorded.- Therefore, the concentrations listed inTable A–X cannot be used to determine absolute amounts of thecomponents. m


TABLE A-X. Results for Experiment#5, TPB- DecompositionTest with AFF/Aq NaTPB

ElapsedTime(davs)o

162429364451586572

107

InsolubleSolids(Wt %)

.———

5.24.54.14.75.46.74.8—-

Concentration (mg/L)*Boron NaTPB lPB Phenol635 138 1980 1073292 -- 1139 819291 -- 1015 1030257 24 765 1079279 22 575 1297284 15 372 1485338 38 148 1797463 28 74 2543200 36 20 1714367 26 22 1989

CS-13’7*(nCi/mL)

——

6371319908

10771459501

1710793

18873800*>~

*These are concentrations of components in the diluted filtrate.The intended dilution factor was approximately x3, but higherdilutions were regularly used after the first sample.**No. dilution.

Experiment #6: New Batch Simulation Test

The purpose of this test was to determine the amount of sodiumtitanate required for the proposed ITP Batch #2 composition andto determine the stability of NaTPB in a second ITP batchprecipitated in the presence’ of a heel of Tank 48H slurry.

This experiment was initiated by D. T. Hobbs in the March 1996 todetermine the sodium titanate requirement (see D. T. Hobbs and D.D. Walker, “Preliminary Results from Radioactive ITP Batch #2Test, “ (U), SRT-LWP-96-O042, April 9, 1996, reproduced inAppendix B) . The following slurry (100 mL) “was prepared in a 120mL polyethylene bottle:

Tank 48H slurry (ITP-236, 1/21/96) 22.3 YTank 49H solution (2/96) 19.9 gTank 25F solution (12/1/95) 23.1 gTank 26F solution (11/8/95) 35.5 gNaTPB solution(AFF/Aquafine, 0.554 M) 6.8 mL

The final slurry was estimated to contain 1 wt % insoluble solidsat 5.0 M sodium ion.

After stirring for one week in the Shielded Cells at ambienttemperatures, the soluble cesium-137 concentration was still300 nCi/g. On 3/14/96,ran additional 5.3 mL of the 0.554 NaTPBsolution was added and the slurry stirred overnight. Bycalculation, this addition of NaTPB produced an NaTPB excess of

i. .

.


TABLE A-XI. Results for Experiment#6, New BatchSimulation Test

Elapsed InsolubleTime Solids Concentration(davs) (Wt ~o) NaTPB lPB

1 2.3192427 2.832 3.639 3.047 3.454 4.061 2.568 1.975(5/29/96)

110(7/3/96)

30101900

16221958130016051694150111431387

86153

36145

1718

<20<20<20

(mg/L) *Phenol

210362

393393339513574551501693

CS-137(nCi/mL)

4.8**

2.4**

*These are concentrations of components in the diluted filtrate.The intended dilution factor was approximately x3, but higherdilutions were regularly used after the first sample.**NO dilution.

10,000 mg/L. At this time the weight percentage of solids wasmeasured and found to be 2.3 wt %. On 3/18/96, the slurry wasplaced in an oven at 50k5 ‘C. Periodically it was removed andsamples taken for analysis. The samples (5 g) were weighed intoa glass beaker and 5 mL of dilution water was added to dilute thesodium ion concentration and dissolve the excess sodiumtetraphenylborate. After stirring for 15 minutes, the slurry wasfiltered. The beaker was washed with an additional 5 mL of waterand the washwater passed through the filter containing the slurrysolids. The combined filtrate was removed from the ShieldedCells for analysis. The insoluble solids collected in the filterwere dried to constant weight. The results of these analyses arelisted in Table A-XI. Because of the washing of the solids andconsequent dilution of the filtrate sample, gamma scans forsoluble CS–137 were not measured during this experiment. However,after 24 and 110 days, a portion of filtrate was removed and thesoluble CS–137 concentration measured.

At the end of the experiment, it was found that the amount ofrinse water used to clean the beaker and wash the solids was notmeasured accurately after the first smple. Rinse water amountslarger than 5 mL were used, but the exact amounts were notmesured or recorded. Therefore, the concentrations listed inTable A-XI cannot be us~d to determine absolute amounts of thecomponents.


APPENDIX BMemorandum Describing Preliminary Results from

Experiment#6

SAVANNAHRIVER T’ECHNOLOGYCENTERJNTEROFFfCEMEMORANDUM /

SRT-LWP-96-O042

Apri19,1996

To S. D. Fink,773-A

From: D. T. Hobbs,773-A and D. D.Walker, 773-A

PreliminaryResultsfrom RadioactivelTP Batch #2 Test

SummaryRecentlyabench-scaletest was conducted intheShieldedCellsofSRTC todetermineifsufficientmonosodiumdtanate(MST) exists in Tank 48H to remove actinidesin the sgxondITP batch and meet the SaltStone feed limit of 18 nCi/g[l]. The results indicate that noadditional MST is required in ITP Batch #2 per the batch plan using waste from Tanks49H, 25F and 26 F[2]. A second addition of sodium tetraphenylborate (NaTPB) wasrequired to reduce the Cs- 137 activity in the liquid phase to below the Filtrate Hold Tankand Saltstone feed limits of 100 nCUg[l]. A complete report will be issued uponcompletion of the testing for organic decomposition.

ExperimentalThe folIowing quantities of tank samples were placed in a polyethylene bottle equippedwith a magnetic stirring bar 22.494 grams (19.1 mL) Tank 48H slurry (ITP-236ATP-235), 20.016 grams (17.8 mL) Tank 49H (ITP-247), 23.041 grams ( 16.5 mL) Tank 25F(sample dated 12/1/95) and 14.502 grams (1 1.2 mL) Tank 26F (sample dated 11/8/95). Tothis mixture, 35.5 grams (35.5 m,L) of inhibited water (0.012 M NaOH) was added and themixture vigorously stirred for 30 minutes. To the diluted mixture, 6.81 mL of a NaTPBsolution (0.554 M) was added dropwise over a 3 minute period. The resulting slurry wasvigorously stirred at ambient cell temperature (ea. 25 “C). After 161 hours (6.7 days), 10nlL of slLIrry was filtered through a 0.45 j.tm pore size disposable Nalgene@ filter. Thefihrate was removed from the Shielded Cells and ar,alyzed for total alpha activity and Cs-137 activity. After standing for 8 days, an additional 5.27 mL of the NaTPB solujion wasadded and the slurry vigorously stirred overnight. The slurry was allowed to stand atambient cell temperature for 3 days and then placed in an oven heated to 70 “C. After 2 Idays, 10 mL of slurry was removed and filtered through a 0.45 ~m pore size disposableNalgene@ filter. The filtrate was removed from the Shielded Cells and analyzed for CS-137activity.

Results and DiscussionThe measured total alpha and Cs- 137 activities for the two filtrate samples are provided inTable I. The total alpha activity after the first NaTPB addition was determined to be 0.48nCi/g, which is well below the Sakstone feed iimit of 13 nCi/g. Thus, it is concluded thatno additional MST will be required in the second IT? batch to meet the Saltstone Feed limitfor total alpha activity.

The test indicated that a calculated 38% mole excess of NaTPB was not sufficient toremove Cs- 137 activity and meet the corresponding Filtrate Hold Tanks and SaltStone Feedlimits of 100 nCi/g. However, after a second addition of NaTPB to bring the calculated

ff”

*- ..


moleexcess of NaTPBio 144Yo,the Cs-i37activity was4.0nCi/g, wtiichiswell &lowthe 100nCtig limit. Possible explanations forthelow cesiumremoval included: (l)overestimation of the NaTPB reagent concentration, (2) slow ~action kktetics due to high Na+concentration, and (3) under estimation of potassium content. A redetermination of theNaTPB concentration confirmed that the value used in the calculations for the quantity ofreagent to add in the test was correct.’ Slow reaction kinetics is unlikely since the calculatedNa+ concentration prior to NaTPB addition was 4.5 M. However, the Na+ concentrationwas not determined analytically. The most likely explanation is an underestimation of thepotassium concentration. The total number of moles of potassium in the test slurry wascalculated to be 2.74 x 10“~.This number was based on on the higher average value fromthe analysis of tank samples and allowing for the measurement uncertainty from replicatedeterminations[3]. However, there could be a matrix effect in the potassium determinationthat results in an under estimation of the true potassium content and, therefore, the amountof NaTPB needed for precipitation.

TableI. TotalAlphaawl CS-137.4ctivitiesh lTP Batch#2TestFiltrates

Calculated Activity (nCi/g)Addition # mole NaTPB/mole K Total alpha CS-137 ~~

1 1.38 0.48 A 0.21 230 ~ 4

2 2.44 not determined 4.0

References1. Process Requirement241 -82H Contro! Room (U), WSRC-IM-9 1-63, revision 6,

January. i 996.

2. R. L. Boyleston, “Cycle 1 Batch 2 Composition”, January 17, 1996.

3. D. T. Hobbs, “Analytical Results for ITP Batch #2 Tank Samples”,IWT-LWP-96-0012, January 29, 1996.

cc: R. L. Boyleston, 706-23CA. W. Wiggins, 241 -84HG. A. Taylor, 703-HM. D. Johnson, 703-56HT. M. Monahon, 703-HB. L. Lewis, 703-8CH. D. Harmon, 7 19-4AJ. D. Menna, 730-2BN. R. Davis, 7 19-4AW. L. Tamosaitis, 773-AR. A. Peterson, 676-TW. B. Van Pelt, 676-ITJ. R. Fowler, 704-2D. A. Barber, 241- 120H

SRT-LWP-96-O042, rev. O page -2-

,?-

R. C. Fowler, 241- 152HP. L. Rutland, 241-152HB. G. Croley, 241-120HW. C. Clark, 241-119HJ. E. ,Marr~ 703-HM. C. Chandler, 703-H ,J. P. Morin, 7 19-4AB. J. Shapiro, 241-119HW. R. Parish, 703-8CM. J. Barnes, 773-AR. F. Swingle, 773-AR. A. Jacobs, 704-TM. Schwenker, 241 -120HA. Patterson, 773-A (LWP records)

April 9, 1996

I1’ ,.

t

0

*

o


Distribution:

Ameri.ne, D.B., 241–121HBarnes, M. J., 773-ABarber, D. A., 241-120HBibler, J. P., 773-ABlue, D. M., 742-6GBoyleston, R. L., 706-23CBritt, T. E., 732-BBrooke, J. N., 719-4AButcher, B. T., 773-43ACardona–Quiles, O., 704-56HCarter, J. T., 241-121HCauthen, G. A., 241-119HChandler, M. C., 703-HChapman, N. F., 704-99sChristensen, A. P., 705–lCClark, W. C., 241-119HColeman, C. J., 773-ACrawford, C. L., 773-41ACroley, B. G., 241–120HCummings, R. W., 241-121HDavis, N. R., 719-4A‘~~~~,~g,t,;,,y.,_Gfi,:703-H;”:.”,..-’

Doughty, D. E., 241-153HDworjanyn, L. O., 779-2AEibling, R. E., 704-TElder, H. H., 704-sFink, S. D., 773-AFowler, J. R., 241–121HFowler, R. C., 241–152HGriffith, R. W., 241-153HGupta, M. K., .732-BHarmon, H. D., 719-4AHobb, D. T., 773-AHoltzscheiter, E. W., 773–AHsu, C. W., 773-AHyder, M. L., 773-AJacobs, R. A., 704-TJamison, M. E., 703–HJohnson, M. D., 704-’56HKeefer, M. T.; 241-153HKelly, J. L., 241-119HLandon, L. F. 704-TLemay, A., 241–121HMiller, M. L, 241-120H

n-

Leung, C., 241-119HLewis,B. L., 703-HL,ex, T. J., 719-4ALong, B. E., 241-197HLott, D. E., 241-197HMarra, J. E., 241-120HMcCabe, D. J., 773-43AMenna, J. D., 241-121HMontini, M. J., 704-sMorin, J. P., 719-4AMurdoch, D. G., 704-56HNorkus, J. K., 73O-2B ,,O’Connor, J. L., 241-120HOrtaldo, J. F., 704-sPapouchado, L. M. , 773-APatel, P. M., 512-11SPeterson, R.A., 676-TPoirier, M. R., 676-TRutland, P. L., 241-152HSatterfield, R. M.,719-4ASchwenker, M., 241-120HShapiro, B. J., 241-119HStevens, W. E., 773--AStubblefield, G.,241-120HStubbs, W., 703-HSuggs, P., 703–HSwingle, R. F., 773-ATamosaitis, W. L., 773–ATemple, T., 703-HThomas, J. K., 730-2BVanPelt, W. B., 676-lTVenkatesh, S., 742-5GVetsch,’W. J., 512-4SWalker, B. W., 676-TWalker, D. D., 773-AWalker, W. C, 241-82HWiggins, A. W., 241-84HWilliams, M. R., 241–121HWilson, R. W., 703-HWooten, A. L., 732-BWright, G. T., 703-HZupon, D. A., 730-BIWT-LWG Files, 773–ATIM, 703-43A

results from tank 48h slurry decontamination and …/67531/metadc687350/... · from tank 49h to...

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