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HW-16076

. UNCLASSIFIED

CHEMICAL RESEARCH SECTION PROGRESS REPORT FOR JANUARY 1950

ByF. W. Albaugh

February 15, 1950

'StCLASSIFICATION CANCELL

DATE FEB 191957

For Tht Atomic Energy Commotion

/?< Qsu ‘Chief, Dtcitnlficatton Branch

Hanford Works Richland, Washington

UNITED STATES ATOMIC ENERGY COMMISSION Technical I nformat i on Sorvico, Oak Ridge, Tennessee

UNCLASSIFIED

Photostat Price S *^0

Microfilm Price S 3 .QQ

Available from the Office of Technical Services Deportment of Commerce Washington 25, D. C.

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C O N FID E N T IA L HW 16076

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PR0GRES3 BBPQRT TOR JANUARY, 1950 CHEMICAL RBSSABCg SECTIOH

I. ntOCESl IMPROVEMENT GROUP (0. F. Hill, Group Leader)

A, RUTHENIUM TBTROXHE DI3TILIATI0HS (K. M, Hannon, C. F. Callio,L. H. Clerk)

Decontamination factors for ruthenium through an ozonization and one

extraction and tvo scrub steps were obtained for distillation times of tvo to

seven hours and for ozone concentrations of from one to three weight per cent in

air. The experiments were performed on successive days, the first at a solution

age of fourteen days. These data, in Table I, show for a six hour ozone treat-k

ment an Increase in the over-all decontamination factor from 2.52 x 10 to

1,1*7 x 10 with an increase in ozone concentration from one to throe per cent.

C O N F ID E N T IA L•I ••• •• • • * •• • •• •• a a •a • • • t•• •

• t • a• • • *it • * •t • • •• •• as •. ss

1 -/mmM N N M r .

R. H. Beaton 2 - HW-16076

T ab le I

RUTHENIUM DISTILLATION, EXTRACTION AND SCRUB DATA „ U n d ilu ted S o lu tion D3-11

O zonizatlon: 0 .1 5 M HNO (as ro c e lv c d ); 95#C .jA ir ■ 0^ so u rce ; Gas f lo v r a t e * 10 cc/m ln.

S olvent E x trac tio n : A cid -d o fic io n t f l o w s h e e t ^D oconta& ination F ac to r

♦ • • ••••♦ • E x p 't .

No.

Age o f S o l 'n . (Days)

V ol.o fS o l 'n .

(ml)w t. i o ,

in Air C ata ly st

D is t 'nTine

(H rs .)•

• •

• •• • • M •• •*..*:

2-23 14 3 2 0.03 M Co** 356

• i »••••••J • 9

• • • • •

2-24 15 3 1 0 .0 3 M Co4* 356 7

2-25 16 3 3 0.03 M Co++ 2356

2 - 2 6 M 20 3 2 C .03 M Co+f 3456

D is tr ib u tio n . C oeff. Ext 'n .f> Ru 1 s t 2nd Otono fc

Unrcaovad E x t 'n . Scrub Scrub T r e a t . Scrubs O v e r-a ll

8 .5 0 .0027 0 .0 9 0 0.22 11 .8 i486 1 .7 5 * io 44 .6 0.0021 0.053 0.40 2 1 .8 2328 5.oe x 10’3 .8 0 .0019 o.o4o 0.30 • 2 6 .4 3720 9.82 X 10*

28.3 0 .0 0 3 0 0 .0 6 1 0.24 3 .5 1740 6 .10 X 10}9.2 0 .0 0 2 8 0.067 0.16 10 .6 2195 2.37 x 104-8.7 0.0025 0.055 0.25 11 .5 2195 2.52 x 10*7.1 0.0027 0.055 0.25 14.1 2050 2 .8 9 x ID4

11.7 0 .0029 0.071 0.20 8 .6 1789 1.54 x 1046 .3 0 .0024 0.54 0.17 15.8 2697 4 .57 x 1044 .1 0 .0 0 1 8 0.046 0.13 24 .4 5270 1 .2 9 x 1C>54 .0 O.OOlfi 0 .30 0 .19 25-0 5887 1 .4 7 x i i y

13.7 0 .0029 0.071 0.27 7 .3 1480 1 .0 8 x 1049.2 0.0025 0.042 0 .21 1 0 .9 3038 3 .3 1 X 1 0 *7 .2 0.0021 0.036 O.lB 1 3 .9 4455 6 .1 9 x ID’6 .2 0.0020 0.042 0 .1 6 1 6 .2 4419 7 .2 x 104

1

\

m9

• •

• • M

• •

• • * •• •

• • • •

..•:M««l

F . H. Boaton

Age o f V ol.ofE x p 't. S o l'n . S o l 'i i . Vt. it O3

Wo. (Days) (ml) in Air

-3 -

Tablo I (concluded)

IIW-16076

Decontamination Factor

2_27(b) 21 3 2 Hone

2-28<b> 22 3 2 0.03 M Ag

2 29<b) 22 3 2 0 .03 M Ag

2-3o(b) 35(DS-llb)

5 2 0.03 M Co

C-30 l4 2 1.9 Roxvo

C-31 15 2 1.3 0 .0 2 M Co

D ie t'n . D is trib u tio n C ooff. E x t 'n .Time t Hu 1 s t 2nd Ozone &

(Hrs.) Unrcnovod E x t’n. Scrub Scrub T reat. Scrubs

3 15 .4 0 .003b 0.072 0.21 5 .8 14384 10.9 0.0028 0.046 0.19 8.3 26535 9-1 0.0026 0.041 0.20 11.0 31456 7 .8 0.0026 0.039 0.20 U .5 3300

2 12.5 0.0016 0.037 0.20 8.0 5440

3 9 .1 0.0017 0 .039 0.21 11.0 47005 7 .6 0.0015 0.038 0.14 13.2 7030

3 23.3 0.0026 0.054 0.14 4.3 30455 12.2 0.0020 0.031 0.13 8 .? 65087 9 .8 0.0018 0.031 0.08 10.2 10718

6 3 .0 0.0024 0.069 0.34 33.3 1704

6 3 .6 0.0021 0.031 0.16 27.8 5625

f

(b)

(c)

C a ta ly s t__ (H rs.) Unrcnovod E xt’n . Scrub Scrub T reat. Scrubs Ovor-aU

8.36 X 1X>3 2.19 x lOj 3.46 x 10*3.80 x 104

4.35 x HI4

5.17 x 10**9.25 x 10*

1.31 *5.33 * 10*1.09 x 105

5.67 x 104

1.56 x 105

P repara tion o f IAFS: DS-11 made 0 .1 M I la jjC r^ , 0 .2 H acid d e fic ien t w ith 10 K NaOB, and then d ilu te d 1:1 v i th scrubE x trac ta n t: Hoxone e q u ilib ra te d v l th e so lu tio n of tho composition: 1.0 M Al(N0oK, 0 .2 H WaOH, 0 .2 M UHH,

0 .02 M Ha2Cr207. “ 3Scrub: 2 .0 M A lU lO jJj, 0.17 M FaOH, 0 .04 JJ UHH, 0.02 M P a tio : IAFS: E x trac ta n t • 2 :4; Scrub-.Extractant « 1 :4 .

The sample o f D3-11 used in experim ents 2-26, 2-27, 2-28, 2-29 vas s to red In s ta in le s s s to o l in s te a d of g lass fo r n in e teen days.

The sample o f DS-11 used in experiment 2-30 was s to re d in s ta in le s s s to e l fo r tw enty-eight days.

1

R. B« Beaton HW-16076-VIn experiments 2-26 and 2-27, the effect of 0.03 M cobalt catalyst versus

no catalyst was studied on 1)3-11, at solution ages of twenty and twenty-one days.

Tho rates of the decontamination factors with and without cobalt was only 1.3 at

thrco hours ozone treatment and increased to only 1.9 after oix hours. Greater

Improvement using cobalt as catalyst (ratios as high as 3.5) has been observed

previously for D6-9 and Dfl-10. These higher ratios wore obtained, however, when

higher ozone concentrations were employed. The catalytic effect appears to be

more marked at tho higher ozone concentrations. The offset cf the catalyet

appears to be the preferential ronoval of a more extractable species.

Comparable decontamination factors were obtained for similar ozone treat­

ments in experiments 2-23 (age of solution, l1* days) and in 2-30 (ago of solution, 35 days). It is significant that the gas flow rate to solution volumo was de­

creased from 3 l/2 to 2 in experl&ont 2-30.Upon examining the data for experiment 2-30, it was noticed that in place

of the usual straight line, the spocioa A removal curvo exhibited a marked change

in slope at about 60£ A unreooved. It thus resembled tho decay curvo for a

mixture of two radioolements of markedly different half lives, and could be re­

solved by the usual method into two straight linos. With each of these linos

representing a first order reaction, it appears that in this oxperimont tho

simultaneous ronoval of two compononts of species A, A^ and A2 has boon observed.A re-examination of tho data for oarller experiments 3howed that 6uch

curves resulted from several distillations using ozone concentrations of 2 weight

por cont or Iocs, but that higher ozone concentrations gave no evidence of nore

than ono component of species A. Tho data arc summarized in Tablo II.

• •• • • • • • • • • •

• • • • •

• •«

HV-16076R. H. B ea ten

T ab le I I

RUTHENIUM DISTILLATION - SPECIES “A” REMOVAL

D S - l l ; 10 cc g a s /n ln ; 95 'C .

1 » •

• i O ,

•-‘‘ga o f f o l 'n . (Days)

V o l.o fS o l 'l l .

(ml) C a ta ly s twt. i 0 .

in a i r 3

In d u c tio nT ine

( a l n . )

( m i n / 1 )

A1 k2

2-23 14 3 0 .0 3 M Co** 2 37 . 0 .023

2-24 15 3 0 .0 3 M Co*4 1 71 0 .064 o.ou

2 25 16 3 0 .03 M Co** 3 ?4 0.032

2-26 20 3 0 .03 M Co** 2 39 0 .091 0 .0 3 6

2-27 21 3 None 2 44 0 .13 0 .017

2 25 22 3 0 .0 3 H A«* 2 39 0 .1 7 0 .0 1 3

2-30 35 5 0 .03 M Co** 2 46 0 .3 9 0 .0 1 4

Of p a r t i c u l a r i n te r e s t v l t h ro sp o o l to s p e c ie s A rem oval a re th o n b a e rv a -

t io n s o f in d u c t io n tim e s , In th o s e r i e s o f ex p erim en ts 2-23 > 24, 25 done on

su c c e ss iv e day s and under I d e n t i c a l c o n d itio n s ex cep t fo r v a r i a t io n s In ozone

c o n c e n tra t io n , th e len g th o f th e in d u c tio n p e rio d vas found to be Inver so ly p r o ­

p o r t io n a l t o th e ozone c o n c e n t ra t io n .

B. HEAD-END FILTROL SCAVENGING (W. 2 . Rooko, H. G. K icks)

1 . E x tra c tio n -S c ru b S tu d io s o f Z irconium and Niobium

In o rd e r to d e te rm ine th e e f f e c t o f c o n ta c t in g v l t h F i l t r o l upon th o

d i s t r i b u t io n o f z ircon ium betw een th e hororw and aqueous p hacca , f u r th e r e x t r a c ­

t io n - s c r u b s tu d io s (IlW-157510 hav« Loon c u rr io d o u t - b o th bo fo ro and a f t e r con ­

ta c t in g d i s s o lv e r s o lu t io n v l t h F i l t r o l . Dato a re g iv e n In Table I I I ,

• • • « •

• • •

R. H. Boston -6- HW-I60'f6

Table III

ZIRCONIUM DECONTAMINATION OF D U SOLVER SOLUTION ON EXTR ACT ION - SCR UB, WITH AND WITHOUT SCAVENGING

Treatment of Dissolver Solution A:

Oxidized vith 0.1 M Na2Cr20y for one hour ut 100*C.; made 0.2 K acid deficient and adik-d to an equal volume of scrub solution. Extraction and scrubs made under acid deficient flowsheet conditions.'a)

Treatment of Di3solvor Solution B:

Oxidized v.th 0.1 M Na^r^Of for one hour at 100°C.; contacted throe timoa vith 20 g/l Flltrcl (1 hour each at 100*C.), decontamination factor !>34; made 0.2 M acid deficient, and added to an equal volume of scrub solution. ExtractJon and scrubs made under acid ioficicntflowsheet conditions/11

Solution A Solution BEh D.F. E*) D.F.a a

Extraction 0.000176 2840 0.0022 230

1st Scrub 0.033 7.6 0.012fb*0.0023

23(b)106

2nd Scrub 0.05 5 0.19 3.1

D.F.' in solv. ext'n 1.1 x 105■

1.7 x 10, 7.6 x lfl4

D.F. in scavenging - 584

Over-all D.F. 1.1 X 105 9 . ! x l<£ 4,4 x 10'

(a) Sec footnote (a) Table I.

(b) Analytical difficulties were encountered, therefore the upper ana lower limits are reported.

•• •• • • • •• • •• 1• • • •• • • • •• • ••• *

• •

4«<» I I I*• I

♦ ♦ • •

t

R. H. Boaton -7- HW-16076

F il t ro l scavenging appears to have l i t t l e effoct on tho over-all

decontamination of zirconium in the solvont extraction steps. Thus, the over­

a l l do contamination factor; including th a t due to F iltro l scavenging, ranges

from 9.7 x lO^.to 4.4 x 10?. These re su lts are preliminary and the exporimont

w ill be ropeated.

The behavior of niobium was followed in tho above run with unscaveng­

ed Solution A. The decontamination factor in the extraction step alono was

1,7 x lO*1. Niobium gamma activ ity was undetoctablo in tho hoxone phase oftur the

f i r s t scrub, shoving an additional decontamination factor of a t least one hundreds

Further studios of niobium aro in process to determine exact figures i f possible.

The high decontamination with respect to both zirconium and niobium

does not agroo with information obtained from Oak Ridgo p ilo t plant runs (QRNL-

463) oven though sim ilar studios with ruthenium have shown good agreonont. A

significant difference between these experiments and the p ilo t plant runs may be

tha t the phases In these studios wore Goparatod by centrifugation. In tho ensa

of niobium, surely, and zirconium, probably, thoro is a radiocolloidal specios

present. Without centrifuging such a specios might bo found in the hoxono phase

mainly because of tho prosonco of small droplets of the aqueous phase, since those

particular radiocolloids aro thought to be preferentially wet with water. Tho

next series of experiments w ill dotormino i f simple se ttlin g resu lts in any

measured difference in tho d istribu tion ,

2. Countercurrent Batch Scavenging with F iltro l

Recent work on the F i l t ro l senvongir^ stop for hoad-ond Rodox food

preparation has demonstrated tho fea s ib ility of a countercurrent batch scavenging

tochniquo with accompanying oconomy in the quantity of scavenger UGod and in tho

storage fa c i l i t ie s necessary for vaoto F il tro l disposal.

• • • • •

• • • M •• • • • I • ft

vi

T

R. H. Beaton -8- HW-16076ir

Dissolvor solution (L6-11) was used a t the pH at vhich i t wa3

rocoivod (-0.12). Tho solution vao oxidized by heating to 100°C. for onu hour

a fte r making 0.1 M in BajC^O^, Consecutive F il tro l contactings of one hour

duration each voro carried out at 100*C, in the manner doscribod in the last

monthly report (HW-1575M • Twenty grams of 100-200 mesh F i l t ro l was used par

l i t e r of dissolvor solution. Tho F il tro l used in tho second end th ird contact"

of one cample of dissolver solution wore used, without washing, as the f i r s t and

second contacts, respectively, of tho noxt dissolver solution sample. Thus, tho

th ird batch of F i l t ro l , F il tro l C, was omployod au the th ird , second and f i r s t

contoct, respectively, of tho f i r s t , socond and th ird samples of dissolvor solu­

tio n . Tho data oro reported in Tablo IV.

Table IV

COUNTERCtiRRENT BATCH SCAVENGING WITH FILTROL

20 g f i l t r o l / l i t o r DS-11 (100 mg/5 ml)1 hr. a t 100#C.

_______Cumulative Adsorption on Dissolvor Solution________F iltro l Samplo 1 Samplo 2 Samplo 3Batch Zirconium Niobium Zirconium Niobium Zirconium Niobium

A 98.2 76.6B 99.7 93. 98.4 77.0C 99,8 58.2 99.6 91.8 98.0 75.51 99.7 ,97.3 • 99.3 91.2I 99.7 97.1

I t has long neon asoumod on the basis op pa3t experiments corricd out

on 100 A scale '(HW-13067) that ono hour heating a t 100*C. was adequate to a tta in

maximum zirconium and niobium adsorption in any single contacting. Noto, in

Table IV, that F i l t ro l vhich has already adsorbed considerable) niobium is ablo to

adsorb as much moro niobium as is adsorbed by fresh F iltro l . For instance, batch

* -

1*•§

, :• • • •

F , H. Beaton -9- HW-16076

C, although already carrying 19.6# of tho amount of niobium found in a frosh

eanplo of dissolver solution, is ablo in the f i r s t contact of the th ird dissolver

solution sample to adsorb 75.5# of tho niobium (compared to 76.6$ for frosh F il-

t r o l) . This offoct, though mashed soaoVhat by experimental lim itations, may

possibly bo present to a small oxtont in the case of zirconium. Thus, further

time of contact studies on tho largo scalo appears to bo in ordor. Longer con­

tac t times can bo to lerated under proposed plant conditions i f tho numbor of

scavenging contacts aro thereby roducod.

C . OXIMTIOK OF PLUTONIUM AJTO STABILIZATION OF PLUrONIUM(Vl) DURING

EXTRACTION OF IAF SOIOTIOKS (C . F . C allis, R . L . Moore)

Experimental work reported by R . L . Moore in HW-12673 has shown that

with repeated batch hoxono extractions of ozone-oxidizod IAF solutions (no holding

oxidant), p a rtia l roduction of plutonium (VI) occurred. Tho E*) values decreaseda

from oxtraction to extraction, and approximately 20# of tho in i t ia l ac tiv ity

romained in tho aqueous phase a fte r tho sixth extraction , vhoroao only 5# vould

bo oxpoctod had 2^ remalnod constant.

Further oxporinwnto have boon completed to determine what concentration

of holding oxidant w ill bo required to provont plutonium (VI) roduction, and to

compara tho oxtraction of ozone-oxidized and dichronato-oxidizod IPF solutions.

A simulatod IAF solution containing 2,0 M UMH, 0.1 g Pu/l, 0,3 M HNO^ and

0.03 M Co++ va6 ozonized with an 0- - a ir stream containing 4# 0 (by weight) for

throo hours a t 95*C. This solution was coolod to room temperature, then diluted

to the o rig ina l volume and mado 0.2 M acid defic ien t. Two samples of th is IAF

solution wore mado 0.04 M and 0 ,1 M In Ns2 r 2®7» rospuctivoly, and mixed with

oqual volumes of a solution containing 0,042 M l)HH, -0.2 M HWO ,. 1.8 M ANN andm

•• • • . *• •• * • ... ••• . . . , , , ■ ,• • • • 1 • ,• » • • * ••• • , • • t . • ,• > • . . . 1 ■ • a * * ,• • «»* • . . . • • .« 1. « • • . . . .«

R. H. Boater. -10- HH-16076

0.01 M flo Cr20 . Thoso IAFS solutions wore thon contacted over a four hour

poriod vlth successive oqual voluiws of distillod protroatod hoxonc which had

been pro-oquilibratod to a synthotic solution containing all components excopt

tho plutcmium. Zirconium phonylarsonato determinations for Pu(IY) wore made on

the IAF solutions beforo oxtraction.

Tho data arc tabulated in Table V and tho oxtraction date are plotted on

semi-log paper as activity versus number of oxtraction in Figures 1, 2 and 3.

Under ncid-doficlont conditions in both the ozono-oxidised and dichromato-oxidizod

IAFS solution with 0.06 M (flowsheet) present some reduction of the

Pu(VI) occurred with a resultant decrease in tho distribution ratio for plutonium.

On tho other hand, with 0.2 M HIJO3 in the aqueous phase, tho distribution ratio remained constant and botter extraction was obtained. Previous determinations

of Pu(lV) distribution coefficients (unpublished data of I, M. Bohn) undor those

conditions of salting strength show a ton-fold incroa3o in tho valuos in going

from 0.2 M acid deficient to 0.2 M HMO3 (ca. 0,04 to 0,4). Tho poorer oxtraction

observed In the acid-deficient solutions i6 e&so consistent vlth tho data from ORNL in which greater plutonium loscoe vero reported in tho acid-doficiont IA

column,

• • I M •• • « •• • •• t* • • •• • • •• • • • • I • • •

•« • ••• • •• • • •• • •• t •• • • •• • t #• •«» ••

i

R . H. Bouton

« •

- 11-

Tnble V

HW-16076

Cone.

mRACTlON BEHAVIOR OP PLUTONIUM HI THE IA COLUMN Comparison of ozone-oxidized and dlchr orate-oxidized solutions

Cone.(4) HNO3 for Each Extraction

J Activity in Aqueous 7 Contacts

(1) Value for six contactings.

(2) Anticipated from graphs assuming constant Eh.a(3) Oxidised for six hours a t &5*C.

(4) Pu(l7) concentration determined by zirconium phenylarsonate carrying.

•

OxidizingAgent

IAF(«A)

beforeBxt'n. K g '

IAFS(M) 1 2 4 _ iL 6 _ L

Prom _8_ Graph

Meos-urod

Antici­pated' 2

. Differ- * ence

• •• M S

• •Si

Ozone o .n .• 0.28 0 -0.2 0.44 0.14 0.04 0.02 0.02 0.007 5«W 4 52• •

• ••

Ozone * 0.11 <• 0.28 0.025 -0.2 0.77 0,58 0.57 0.60 0.44 0.37 0.40 5.9 2.1 3.8

i . Ozone 0.11 to .2 8 0.055 -0.2 0.80 0.75 0.74 0.69 0.67 0.60 0.58 0.73 2.9 2.2 0.7? • t

• • •• • •

• •e ♦ •

• • • H&2Ct2®7^^ 0,22CO.11 0.055 -0.2 0.85 0.77 0.74 0.70 0.58 0.62 0.58 0.52 0.74 2.8 2.1 0.7

• • • B^ J L ( 3 ) 0.22 <0.11 0.055 0.2 0.87 0.63 0.87 0.82 0.83 0.83 0.76 1.8 1.8 n il

c/ta/50 XHW-16076

. .-.3 .\ : £, KULiER; .QF[ a{J0HAroiN

c/a/50

>

-13- BW-16076

HEXONE EXTRACTION OP UPS

0.2 U HKOj in aqu«ou«

c/m/50>

PIOUHE 3HEIOKE EXTRACTION OP 1AFS

o!o25 MKa^Cr^ as hol« Acid dsfioisnt conditio]

’tr.j

Htf-16076

R. H. Boaton -15- HW-16076

I I . PROCESS STUDIES (C. M. S lan sk y , Group le ad e r)

A. IRECIPHATION OF FLITTONIUM (IV) IN REDOX lirRF (L. L. Burger)

Experience a t ANL has shown th a t IIBF stream s which are allow ed to

s tand w hile s a tu ra te d w ith hexone may form a p r e c ip i ta te which is la rg e ly

Pu(lV) o x a la te . Evidence p o in te d to the im purity m ethyl Isopropyl d ike tono as

being th e m a te r ia l re sp o n s ib le fo r form ation o f th e p r e c ip i ta te .

Removal o f the o rg an ic so lven t by sparg ing appears to e lim in a te th e

d i f f i c u l t y . The p r a c t ic a l problem is to determ ine the p o rtio n o f th e hexone

and /or th e d iketone decom position product which must be removed to in su re

a g a in s t plutonium p r e c ip i ta t io n . As l i t t l e as l^ o f th e s a tu ra tio n amount o f

hexone, i f a l l converted to o x a la te , could p r e c ip i ta te apprec iab le amounts o f

P u (H ) , however I t is f e l t t h a t th e p ra c t ic a l l i m i t nay bo w ell above th a t

f ig u r e . A few experim ents have been designed to a s c e r ta in the c o n c e n tra tio n

l im i t s .

To sim ulated IIEBP s o lu tio n s (HW $3 f lo w sh ee t, ca^ 1.1 M HNO ) d i f f e r ­

en t amounts o f diketone and hexone wore added. P re lim in a ry r e s u l t s a re :

(1) Diketone p re se n t a t a co n cen tra tio n o f 10 gms/L gave a p r e c ip i ta to

in 3-4 hours a t 85*C. which removed th e g re a te r p a r t o f th e p lu ­

tonium from s o lu t io n . (Using thorium a3 a s ta n d -in , a p r e c ip i ta to

was obta ined in two days.) These r e s u l t s confirm the experim ents

a t ANL.

(2) At a d iketono co n c e n tra tio n o f 1 .0 gn/L i n i t i a l t e s t s shoved no

p r e c ip i ta t io n in 48 hours a t 85*C. Theso experim ents w i l l be

repeatod us th e re i s somo questio n as to the v o la t i l i z a t io n o f

d iketone from th e re a c tio n f la sk s d u rin g th e f i r s t th re e to fo u r

hours.

R. H. Beaton HW-16076-16-

(3) No p r e c i p i t a t e h as boon o b ta in e d w ith 1$ by volume pure hexone

in IIIB P s o lu t io n s a t 85*C. o v e r p e r io d s up to 48 h o u re . Thera

i s ev id e n c e o f complex fo rm a tio n , how ever, aa th e Pu(IV) band

I n i t i a l l y a t 477 By*. in PuOlO^)^ s o lu t io n s i s s h i f t e d t o about

486-488 in a b o u t one hour a t 85*C.

B. ABIABAT1C a t mOH TUB HEKOWS - MCTIC ACID REACTION (B. R . Jones)

The r e a c t io n o f 0 ,5 M HWO3 in hoxono was c a ta ly z e d by making th e so lu ­

t i o n 0 .1 M in HNO2 and th e j t (*C .) moasurod in a Dover f l a c k . The c o n d itio n s

ro p ro s o n t th e bohav io r o f I M o r IIIAX in th e e v e n t o f g ro ss c o n tam in a tio n by

a re d u c in g a g e n t. The r e s u l t s a re g iven in T ab le V I.

T a b le VI

HEAT OF REACTION OF 0 . 5 M HNO3 H7 ffiXOHE WITH 0 ,1 M HNO AS CATALYST

0 houro 6 hours 24 hourb

O bserved tem p era tu re (*C .) 27.7 30.1 3 1 .1A d ia b a tic to m p era tu ro r i s e (*C .) 0 15.2 22.6

(M HNO3 0 .5 0.256 0 .1 3 2M HN02 0.10 0,026 0.009

It HNOj re a c te d 0 5 0 .5 ■ft. 5

O rg. a d d s form ed ac a c e t ’ c , g / l 0 » 4 .0M o thy lisop ropy l d ik e to n e , g / l 0 3.56 6 .1 5D ln ttro ls o b u ta n o , g / l 0 1.69 2 .7 7

I f comp lo ta r e a c t io n o f th e HNCL were assumed th e l im it in g te m p e ra tu re r lo e

( a d i a b a t i c ) based on th e s e d a ta would be 30.5*C.

C. TBP METAL RECOVER* FROCKS*)/v>-V 0

1 . So l u b i l i t y o f TBP in Aqueous S o lu tio n s W 0*4.Cm*. Ce

The s o l u b i l i t i e s o f vacuum d i s t i l l e d TBP in w a te r , 3 M HNO3, 6 M

RNO^, 1 M UNH and RAW (0 .1 9 4 M Ka^LO^ 0 .176 M Na^POt, 1 .96 M NaNO^, 3 .0 M HNO3)

R . H. Beaton -17- HW-16076

wore measured a t 2^*C. The s o lu b i l i ty o f TBP from 1% by volume TBP in Deo s

Base vas noasu red in th e somo s o lu tio n s as above a t 25 and 50*C. Tho r e s u l t s

are given in Tablos VII and V II I .

Tablo VII

GOLUB ILITY OF PURE TBP IN AQUEOUS SOLUTIONS AT 24*C.

M ucous Fhaso r/1 TBP

Wator 0 . l 4

3 M HNO3 0 .3 56 M HN0-, 0 .2 81 M tUVH o ,o 4RAW 0 . 1 0

T ablo V III

solubility o r tb p fbom i % by volume

TBP • CEO BASK IN AQUEOUS SOI UT TONG

Aqueous Phase ( t / l TBP a t 25*C, « / l TBP a t 50*C.

H ater (0 .1 4 ) 0 .18

3 M HNO3 0 . 2 2 0 .3 06 M HNO3 0 .1 3 0 . 2 2

1 M UNH 0 .0 4 O.lBRAW 0 . 1 2 0 . 2 0

!. E f fe c t o f TBP Im p u ritie s upon Ur&nyl N itra te D is tr ib u t io n (l.M .Rehn)

D ata ob ta ined from b a tch co u n te rcu rren t a t t r a c t i o n s tu d io s r e ­

vealed somo d iscrepancy iu the uranium d is t r ib u t io n s o f th e RC column. High pH

values o f tho aqueous phases and p o s s ib le im p u ritie s in th e TBP wore checked as

po ssib le causes o f tho tro u b le . The* fo llow ing s e t of d i s t r ib u t io n measurements\

in d ic a te s bo th im p u ritie s and high pH to bo d e trim en ta l t o s tr ip p in g in th e ono

to ton g ra m /l i te r UNH re g io n , f i f t e e n por cen t TBP by volume vas used for each

jr.porim ent. The same Doo Bano and e x tra c t io n cond itions voro m aintained in oach

ts »«• • t •».. »• •• • M

: ; : { . : r i : l i t«• id • < I •! •• *•M0m‘» m-iinr i r r 1-

. »•. • 1:* : t* , • i• i« •»

MSW&yMnWS t

R . H. Beaton HW-16076- 10-

caso bu t th e TBP q u a l i ty v a r ie d as fo llo w s :

TBP #1 - Puro vacuum d i s t i l l e d , p re p a re d in t h i s l a b o r a to r y .

TBP #2 - C om m ercially d i s t i l l e d , ns r e c e iv e d from Com m ercial S o lv en ts Co.

TBP j?3 • S to re d moro th an two y e a rs In m e ta l, p u r i ty unknown.

TBP #4 - Same as #2 b u t t ro a to d f iv o m inu tes w ith IiaOH polletB.

TBP Ifo - Same as #2 b u t u sed and re-U B ed s e v e ra l tim es In th o pu lso column (sodium carbonato and v a to r w ashed).

TBP #6 - Same a s ^2 b u t t ro a to d two wooks w ith NaOH p o l lo t s fo llow ed by w a te r wash.

Tho r e s u l t s o ro g iv en In T ab lo DC, The vacuum d i s t i l l e d TBP has a

v e ry low which fa v o rs low RCW lo s s e s and compares fa v o ra b ly w ith commercial

TBP (Commercial S o lv e n ts C orp .) which hao boon vashod w ith 2 M Na^CO^ o r in

c o n ta c t w ith s o l i d NaOH fo r a s u f f i c i e n t t im e . Commercial TBP (ao roco ivod)

c o n ta in s an im p u rity which changoo th e E° by a f a c to r o f abou t 100 in th o d i lu te

re g io n and by abou t fo u r in th e 10 g / l UNH r e g io n . Tho b e h a v io r o f 0 .01 M HNO

in PCX i s to d ec ro a so th o o f UNH f o r e i t h e r source o f TBP.

C a u s t ic o r carbonato w ashing o f o rg a n ic e x t r a c ta n t sh o u ld bo ade­

q u a te t o remove* c o m p le tin g im p u r i t io s . T h is would bo done on a l l f r e s h incoming

TBP.

T h i b e h a v io r o f TBP In tho above experim en ts w a rra n te d a chock on

th e beh av io r o f t r u c e amounts o f norm al b u ty l a c id phosphate on tho E^ o f UNH,

Vacuum d i s t i l l e d TDP v ac d i lu te d t o 1*^ by volume w ith Doo Bane and sp iked w ith

0 .2 and 1 .0 g / l o f a 9 0 - ‘>0 m ix ture o f mono and d ib u ty l a c id p h o sp h a to s . T his

phase was c o n ta c te d w ' t h on aqueous phano o f 1 ,0 or 10 g / l UNH, Thu r e s u l t in g

d i s t r ib u t io n s o f UNH a re givan in T ab le X. Tho b ehav io r i s vo ry s im ila r to t h a t

observed In com m ercial TBP.

R. H. Beaton -19* HW-16076

T ab le IX

DISTRIBUTION COEFFICIENTS OF UNH IN RC COLUMN

A. E ffe c t of Source and Treatment

ireo o f TBP1 g / l UNH in Aq.AJUJ25 _lL_

10 g / l UNH in £q, Aq, pH Ba

TBP i/1 4 .5 0.019 3.00 0.025TBP #2 4 .5 1.143 3.00 0.106TBP #3 4 .4 0.76 3.00 0.040

TBP #4 4 .1 0.951 3.00 0.140TBP i/5 4 .5 o.oo84 • »TBP f 6 3 .6 0.0027 3 .4 0.019

B. E ffe c t o f 0 .1 M Acid Added to Aqueous, 1 g / l UNH

OrganicNo Acid

p H o f Aq. ' e!0.01 M

pH o f Aq.HNOj

i n

TIP #1 4 .5 0.019 2.2 0.0062TBP #2 4 .5 1.143 2.2 0.59TBP #4 4 .1 0.951 1.8 0.76

Tho decom position o f 15# TBP (vacuum d i s t i l l e d ) in co n tac t w ith a

4 M aqueous phase fo r 20 hours a t room tom poraturo vas measured In term s o f tho

change In E* o f UNH. With 0 .8 g / l UNH and 12.0 g / l HNO3 (pH - 0 .8 ) In the

aqueous p h a se , th e Ea was found to be 0.2 * 0.1 which is In good agreem ent v l t h

puro TBP v l th tho same amount o f a c id in th e aqueous phaau, A pparently tho dogroo

o f h y d ro ly s is to a c id b u ty l phosphates was n o g llg ib lo .

Tablo 1EFFECT OP NORMAL BlfTYL ACID PHOSPHATES

ON m o E n OP UNH IN ABSENCE OF SALTING AGENTS

g / l Acid Phosphates In

I n i t . Or«.uim

A m ecusSo,d i i J g

15* TBP in Oao Base UNH HN6t>« / l g / l e! (UNH)

0 1.13 0 .3 3.7 0.022 0.07 0.0200 .2 0.75 0 .3 2.7 0.20 0 .1 0.270 9.5 0 .5 3.4 0.20 * 0 .1 0.0211.0 7 0 .6 2.3 3.0 0.17 0,40

R . H. Boat on - 20 - HW-16076

3. Batch C ounter c u rre n t S tudios ( I . M, Rohn)

Two b o tch co u n te rcu rren t e x t r a c t io n s tu d ie s v l th TBP were completed,

ono v l th CCI4 as d i lu e n t and th e o th e r Boo B aso. In WR-18 th e e x t r a c ta n t was

1% t y volume TBP (n o t p re tre a te d ) in CCI4 . T h is run was id e n t i c a l In a l l o ther

o p e ra tin g co n d itio n s t o Run VR-17 w ith TBP - Deo Base p rev io u s ly re p o r te d .

Loseos in RAW w ero.low er w ith CCI4 th a n w ith Deo Base, but RCW lo s s e s were about

th e same. Those d a ta a re sunnarlxod in T ablos XI, X II, X III , XIV,

In Run WR-19 w ith concon tra tod RAP, th e incroaso in s a l t conten t

and uranium c o n c e n tra tio n was balanced by in c re a s in g tho organ ic flow w ith very

s a t i s f a c to r y RAW lo s s e s . In f a c t , s ta g e s 9 and 10 were su p e rflu o u s .

Tho fo reg o in g d iscu ssio n on ?BP p u r i ty would in d ic a te RCW lossos

in thoso s tu d io s o f th o o rd e r o f le s s th a n 0 .1 had p re tro a to d so lv e n t bean usod.

T h is i s v e r i f ie d in Run WR-12 (HW-15453) whero puro TUP was u sed and tho RCW

lo s s in f iv e s tages was 0 .0 4 $ ,

Table XI

RAX:

RA3:RCX:

BATCH COUTORCURRKNT EXTRACTION STUDY WR-18 NORMAL COMPOSITE URANIUM WASTE

15% by volumo TBP in CCI4 » 1.W375, no p ro treatm ent

3 .0 M HNO3 Water

RAF: O.1B8 M U0£+, 0.I8 H GOj;,0.18 m“por, 4.18 m no; ,2.71 M Na% 2 .00 M

^ * 1.2274

Flow Volumes: RAT.jRAF:RAX:RCX » 10:20:25:20

Product Streams a f t e r 46 C on tactsrtT a l l 1M g /l.jg K h Volume ml U lo jk ca (1 o f

RAW l.ll*?!* 0 .0u^6 13?.32 30.0 0.005RCW 1.1(675 0 .61 1.10 2U.5 0 .6 6?cu 1.0690 95 11.97 20 .5

A nalysis o f Streams a t D if fe re n t C ontactingsbo. o f Throughputs 2T 35 ___ 39 43 )i 45

? / l USH in RCU 92 .0 92.9 93.2 92.3 93.8RAW 0.010 > 0.0081 0.0001*7 0.00037 0.0088new 0.66 0.52 0.62 0.64 0 .61

W&Mi

R . H. Boaton

• l«l••••••• « *

»

« •• •

• «*•*

• ■ • «• •« i > *» *

• :•••••

• :

S tage

I 2w 3

Fo«d 4

5* 6 41 7

8 9

10

8*g4J3

I

ft. 12

(0 14

“ 21"

T ab le XII

STACK DATA - V*-l8

Solven t: CCI4 - 15# TBP, Sp.G r. 1.4875

Scrub: 3.13 M HR03, Sp.Q r. 1.0997

HW-160T6

Food: 0 .188 M UCtf4 . 0 .18 M 80?,0 .18 m“ po |7 4 .18 h f c : /2 .71 M Na*, 2 .00 M H .

« 1.2274 •

\m m °3 I T " UNH HHO3 PH PojJ s o : K

1.5212 « 12.00 1.1070 11.*1 20*.98 -0 .1 * m • .1.52*1 73.83 U .0 3 1.1009 13.02 197.6 -0 .1 * 0 .52 - 5.67 8 .6 41.5263 7*.3 8 .8 7 1.1099 1*.87 193.1 -0 .1 2 m 0 .7 0 5.00 3 ,1 1

1.5275 87.97 8 .1 7 1.1693 32.00 1*9.9 -0 .1 0 12.0 13 .3 2.75 5 .1 3

1.50*1 22.02 12.98 1.15*0 6 .* 7 190.15 -0 .1 0 13.0 , 1 * .9 3.*0 1.231.W 57 7.08 17.87 1.1517 0 .7 * 153.51 -0 .0 8 13.0 13 .6 9.57 2.701.U837 1.20 18.17 1.1513 0 .1 0 153.99 -0 .0 8 12.5 13 .* 12.0 3.051.W 37 0.16 17.57 1.1519 0 .0 1 151M -0 .0 8 13.1 11.9 I6 .0 4 .081.W 62 0.019 17.29 1.1505 0.0032 1*0.16 -0 .0 8 12.* • 5.9* 1.56i .h rm 0.0018 17.** 1.1*5* 0.00*16 138.32 -0 .0 6 13.0 12.4 0 .39 0 .1 1

1.50*1 28.*0 1.72 1.0650 95.*9 11.97 *0.78 0.006 0 .1 6 0.297 * .5*l.* 9 2 0 8.26 l .» 2 1.033* 53.1* 2.12 1.91 - ** 0.155 9 .7 2l.* 8 9 5 l .* 5 - 1.00*5 «» 2.00 2 .8 2 - 0 .0 6 «■»

l.*80O 0.72 0 .80 0.9978 0 .5 5 • 3.50 0.00* - 1.3 *10*l.* 8 7 5 0 .61 1.10 0.9972 0 ,16 - 3 .81 - - 3.8 >105

d S noosuromonta were made lo s t on samples and may bo s l ig h t ly la v .

$$$&&&&*$!&$& £ . • +y t ' l V i ' i 7

i

«I• i

R. H. Boaton “ 27r HW«l6o?6

Table XIIIi

STACK DATA - HB-19

BAX: 15* TBP In Duo Base Food: 0.29 M UOt*, 0.29 K &0||,0.31 5 PO|, 6.27 M BO3,

Scrub: 4.0 K HHOj 4.42 H Ha1, 2.73 M H*.. 1.3812

„ „ Organic (g /l) Aqueous (g /l)

r Stage

•9 *

UHH HHO-4

TJBH HNO PHH

S0| K. . . . A.-

K■ * * * * •

: *: 0.Q668 64.53 9.58 1.1423 14.36 260.78 -0.24 0.49 t e* 4.49 3.01♦• » 2 2 0.8682 73.64 9 • 30 1.1423 20.37 256.04 -0.24 m 0.1 3.62 3.29

»«#*•* ■ j <8 3 0.8695 85.33 9.25 1.1455 19.89 263.06 -0.29 0.49 : 4.29 5.52* • • * *

$ 0

| t * \

Food 4 0.8694 81,63 9.13 1.2759 48.20 206.46 -0.46 m - 1.70 1.18• « *

I . tI 2

0.8M5 40.49 18.83 1.2565 6.46 213.42 •0.41 - 1..5 6.26 1.475 • « » « » . 0.8250 5.99 26.16 1.2522 0.66 213.58 -0.37 * ■ - 9.07 1.15

« . - « » •

• : S 7 0.8213 0.42 27.09 1.253H 0.061 215.73 -0.28 19.8 • ** 6.09 0.803f. 0 0.8203 0.071 2,-.85 1.2530 0.00B1 212.56 -0.28 - - 3.77 l.o4

t-: *«*••• : • :1 r*°s £ «»**

a 9 0.8209 0.012 26.52 1.2539 0.0056 212.15 -0.28 - 18.4 2.14 0.254f* 10 0.8200 0.0016 25.05 1.2412 0.0024 187.21 -0.24 - 0.67 0.093

u 0.8507 60.97 1.8 l 1.0785 114.7 15.0 *0.6 0.13 m 0.532 6.673 1 2 0.8337 34.86 4.73 1.0548 89.22 1.19 1.9 • » 0.391

0.24016.70

iI k

0.8166 11.13 1.79 1.0292 *»6.4l 0.22 2.49 0.13 26.70.8102 1.41 0.57 1.0070 14.73 0.13 2.84 - - 0.096 8O.5

I M m M& 5. ; . •• - .

1 ' : - S f ‘ ■ i l i : - ;

15 0.6092 0.55 0.38 0.9904 l.o4 * ’ 3.41 0.53 * •

Ift

R . H. Beaton -2 3 - HW-16076

T ab le XIV

BATCH COUNTERCURRENT EXTRACTION STOW Vffl-19 CONCEWERATED COKFOSITB URANIUM WASTE

RAX: 1$4 by v o lu aa TBP (Conm ercU lS o lven ts C o rp .) In Deo Base

HAS: 4.0 H HHO3

RCXt W ater T, P . - «8*C.

RAP: 0 .2 9 M UOj*, 0 .2 9 M SOj, 0 .3 1 M POjj, 6 .2 7 M NOj, 4 .42 M Na*, 2 .7 0 M H*.

4 2 . 1.3812

Flow V oluaea: RAS:HAF:BAX:RCX = 10:20 :35 :23

P ro d u c t Stream s a f t e r 54 C on tac ts

« v f./ i inra k/ i HNO, Volume ml U lo s s e s a o f RAF)

RAW 1.2412 0 .0 0 2 4 167.21 29.5 0 .0 0 2 3RCW 0.0092 0 .5 5 0.39 35.5 0.62RCO 1.0705 114.7 15.00 25.4

A n a ly s is o f 31 roams a t D i f f e r e n t C o n tac tin g s

No. of Throughputo 36 42 46 50 52

g / l UNH in BCU 113.2 110.9 113.5 113 .5 112.9RAW 0.0023 0 .0047 0.0032 0 .0 0 2 9 0,0018ROW 0.47 0.62 0.62 0 .2 4 0.45

4 , N i t r i c A cid Recovery and W aste C o n c e n tra tio n (R . M. Wagner)

The c o n c e n tra t io n o f th e w aste s o lu t io n (RAW) from th e TBP p ro cess

vaa fo llow ed from th e s ta n d p o in t o f f r e e s in g p o in t o f th e r e s id u e and HNO3 r e ­

c o v e ry . Both b a tc h and con tinuous ex p e rim e n ts were perform ed on a o im ulatad w aste

s o lu t io n composed o f 0 .1 9 4 H NaHSOjp 0 ,1 7 6 M H3PO4 , 2 .68 M IfaNOj, 3.28 H HNO3 and

a ^ O f 1 .2545.

a . B a tc h S tu d ie s

One l i t e r samples o f RAW were f la s h e v a p o ra te d a t 760 and a t / "

10 mm Hg p r e s s u r e . D ata f o r cum ulative p e r c e n t HNO re c o v e re d v e rsu s cum ulative

P i . cen t overhead a re g iv en in Table XV. From th e se d a ta l i ^ i id - v a p o r e q u i l i b r i a

have boon computed and a re shown in F ig u re 4 .

a ,

: . r: : :> • » . *

H« * . •. 1 • t* t. :

: : : s ,* ♦. . . »•

R. H. Beaton m2\~

Table XV

HW-16076

Flash evaporation of 1AW so lu tio n a t 760 m taken In one degree cuts

Vapor Temp. N UNO? Cumulative % A vailable Cumulative VolumeCut r e . 3 in Cut HNOi Recovorod of D is t i l la te (ml)

1 100 - 104 0.19 0.61 106? io 4 - 105 0.25 1.28 1*43 105 - 106 0.41 2.41 2854 106 - 107 0.62 3.25 330

5 107 - 108 0.64 4.33 3726 106 - 109 1.13 5.89 4127 109 - 110 1.49 7.53 4373 110 - 111 1.94 9.71 474

9 111 •• 11? 2.54 11.96 503v ^ 10 112 • 113 3.22 14.52 529

a 113 - 114 3.99 10.15 55912 114 -1 1 5 4.85 21.71 580

13 115 - 116 5.94 29.13 62114 116 - 117 7.70 46.85 70515 117 - 118 9.02 59.57 74416 118 - 119 9.89 69.21 77617 * 119 - 120 10.20 97.24 866

Residue 51,37 gn n i t r ic ac id (45.25 g unavailable) 100.lOf* Mat. B al.

Vaccum d i s t i l l a t i o n v lth 1AW so lu tio n a t 70 ran p ressure v i th no f ra c tio n a tio n .

Cut Vapor Temp. N HNO Cumulative # A vailable Cumulative VolumoCut (* c .) in Cut HNO* Recovered of D is t i l la to (ml

1 o - 55 0.86 12.86 4902 53 - 58 0.96 l4 .o8 5323 58 - 61 2.16 18.28 5964 61 - 64 4.21 27.52 668

5 64 - 66 8.73 54.65 7706 66 - 70 12.55 74.54 3227 70 - 77 13.07 84.90 848e 77 - 6z 13.37 98.43 881

K*« idio 48.10 gn n i t r i c a c id (45.25 g unavailab le) 99.05* Mat. B al.

•• «»• * ♦S i r i iI f t.. v

\ j • •/ **'

j i u : : : : :: » ... «» .

IKX

SI ,<

U3T

3IH

UK

KO

liOTJ

U *

10*

I

-25- W-16076

0.3 0 4 0.3 0.1I90LS FfUCTIOH HITRIC iCID I I POT

V r t f W * v • r T & v ’ . r ^ ' »•; • •

-J*- » 16076

A l i t e r of HAW v%£ next boiled dovn to 33$ of He orlgi&el

voluas under a four p la te bubble coluaa, and thee sparged v ith steon v tth no

fractionation u n til o:w l i t e r of ctoaa tod been cormuwd. The object of thi*

#xj»rl»m t vae to get high HSO recover!«s but to hare e low freesu*g point in

the po t. The &VO3 recovery vus 08.5$ of the available £10,; toe resulting pot

residue, afior neutralising to s pH of 1£ v ith 50$ tfaOB, had a f .p . »u*d voluaa

of 3 /C . and 4^0 cc, respectively. The voluas roes to 640 c: by diluting to s

f .p . of 417*0. The fin a l solution ted a density of 1.3* 13 and viscosity of 15.23

a illipo iso* a t 2j*C. The solid phise a t roos teapereture vw found to be onhy-

dr<>uaHAW v»-i then batch d i s t i l l e d With t 25 p la ts fra c tio n a tio n colusan.

one inch d 'aao te r x 28' long ar.J pnek-id w ith 1J C " d iaao tw Konake to l ic e s . Tta

r e f lu x ra t io van 3 and tho pressure 760 m . Tbs run vas cor.tU m d u n t i l nsar

dryness of tbo residue .g iv in g recovered 'LIO v i th an over a l l concen tra tion of

11.0 M, but e m jo r t ty o f th-j caao ovor a t a concentration o f 13.5 M* Pre­

c ip i ta t io n of s a l t s in th e b o iling pot took p lace as the concen tra te \ EMO s t a t e d

cooing over. harp ies o f 347 s ta in le s s s to e l and Carpenter 20 In the s t i l l pot

abovv-d corrosion r a te s over 26 hours of 15,2 and 3.5 a ila /y o c r p en e tra tio n ,

‘M sp e c tiv ily . The r e s u l t s aro givon in Table XVI.

Table XV:

HATCH mCflCHATlOB OF 0K2 LITER OF BAH A? 760 na

Cutti WO* in Cut

Cm HHO CuMilatlvn Per Cantin Cut* Available HNOa Recovered

Cunulativu Vol. Recover*

1 0.002 0.032 0.012 250 cc2 0.003 0.048 0.037 5003 0.011 0.065 0.073 6J04 3.53 17.3'* 8.46 67C

5 13.33 84.03 49.12 7736 13.77 86.70 91.04 8787 15.37 7.75 94.32 886

Residue 55.0 (44.29 g un­available 1.

• s s s t • ♦• • t • • *• • • • «e s s •• 4 S • • «• • ••• • M »

& » :A i V , V ^ ' ‘M & W * # * * * * * * ” ™ " • * *

99.63 Mat. Bal.

« ( • • • • s e e • • • • Mr * * • s s • • • #* * i i e s s • s i * tt . . • * • •• a a . . . . . • . . . . .

' — -l-»- -. .vM >*W»

n

t U U m t H W * * ' ' . w — -•

H. B. Beaton EV 1607627-

A batch d is til la tio n s ta l ls r to tho fDragging vw perfomod trltfc

tbs exception tha t 29 ml of concentrated sulfuric acid v*rc added to tho In i t ia l

R-*W; Uu K SOj* m i >qulval*ct to the to ta l FO{ and 30{ m tho original 1L‘H. Tbs

resu lts vara a la lla r to the pravtou* run* v lth tbs exception that 9 7 of tho

In itia l 4 K K»C>3 wu rocororcd in 915 n l of d litlU a to of vhlch 93<> was 12.7 M

23*0 . The ana* spocinen* of ita ln la a s stool shoved about one half the corrosion

ra ts as before.

b . Continuous gvapor a t ; on

A boiling flask %ms f i t te d v lth a liqu id in le t and outlet and a

vapor take o ff v lth a aininua of reflux and to ta l condensation. IStor attainment

of oquilibrlua the B.P. and f , P. of tba pot and par cant HSO rocovertd In the

d is t i l la te wore acasured for four different vclune ratio* of food/distlllat-,;.

The re su lt# arc g lv -n in Table XVII,

Tnblo 33TII

corraroo® fuscw sxjb of juu with 3 .aa r a u s /in s a ■•.v..iL.au:

♦ .'.VBlla'blo Resliluo Vol. R.slduo aftor Bout.Voluaa Ratio H HNO. ia In BKh RTpT T X ' * T v N t S

;.‘!»tlUatc/RIN S la tlllr tc D istilla te (*C) CC) * of RAW - F.P. 30* F,P.

0 .5 0 2 .0 1 3 0 .6 84 U 3 U!> as 9*0 .6 0 2 .9 2 53 > 96 1190 .7 0 3 .3 6 9*».l 121 121 30 120 46

Tho cvallablu BtOj Is based on tho ox.stunco of pho*phato and

sulfatj as HjPOh and HaHSCty. These salt* in tho presence of a large anount of

KaHO at tho concontratlon* encountered her- do not liberate appreciable anount*

of KEO3 in the vapor phase at the B.P, The rocovjry of IIBO is very good at tha

higher salt content of tho pot, and tho operability and volusu reduction excellent.

ft. a Batten -;ft- 1M6076

Tt 133 *0iuftj* of RAW are produced par 100 of easpotUo ur**uus waste fro* the

tunic, than tho dhow sveporotor rattan.* aft*4r available HBO^ rvcevery

followed by neutralUatioa with 5 # BoQH and dilution to t f.P. of *3^0, etc bo

returned to the storage tank* without further concentration. I|mmr« tine*' the

swutrol solution can bo ovnporatad after being transported to U w tank firm a

fUftlnr reduction can be roidily obtained,

3. frogling K>lnteTfco pot residue iron tha RAV concentration cui ha troetad in a

rubber of ways. If !t It to b« transported through pipelines, tbz fronting point

can ho reduced to sosu satisfactory value by either direct dilution or by neutral-

nation nth caustic followed by dilution. Since it.xnlose steel la generally

uajd, ttio neod of a pH of about 10 it not needed to control corrosion. In fact,

Uw jrlnelpol cone 1 deration nay VjII be to kaep the volunt at a cintrain. It a pH

of 10 vm have found JlajHPO to ba tbo solid phase vbich hat a relatively low

•oiubtlity. The desirability of neutralising to lover pH vcluea where Ha HPO

is the tolld pheso or to dilute the residue without caustic addition is boing

investigated in cornu detail. The dlff icultios encountered by the precipitation

of gelatinous precipitates at a pH of 10 such os Fe(0H)j may alto indicate dllu

tion at higher actditlos. Obviously acid solutions con bo o&do alkaline at they

jtUr the final storage tank*,

III, W/j Tg TR2ATKZNT (F. J. L.iU, Croup Loader)

A, METAL HASH KBCQvaTC BX TRIETTYL PH0rPHAT& SOLVaTT Sm/vCTIOM (R.L.Mctrt)

1. Decontamination Studies - Tracor and Full Hanford Luvol

Preliminary studios wora carried out with tirconium tracor containing

an undetermined amount of niobium, A 3 M ENO solution of thio tracer was con­

tacted at roan temperature with an ugual volune of 1% TBP - Deo Btso. Shonka

. . . . . > 1 1,*« . • ..1 , • . . •• ••.. . .<■ .1 • ••• • • • •

a. a. fttetott w-16076

ae im rs—ttt» indicated c i j of the « * » ac tiv ity w a in the organic phase on

se ttlin g ; £*, W,3l, on centrifugation of tbs tvc phases, Addition of 1 g / i of

a m i tu v fluoslU cate to the aqueous phase reduced the gams activ ity transferred

to the organic phase to O.TJk Thus the presence of fluosU lcato improved the

decontamination v ith respect to gasoa activ ity by a factor of ca* $. ..luturrui

absorption studies of th : organic phases indietied qualitatively tha t fluoslU cate

improved iircoa:us decontamination aare than i t had niobium doconto*'.nation, fross

beta decontamination being improved by ft factor of co^ 1}.

/. synthetic current aotol v&stc solution (Oil) acid ified to k H IDOj

vna spiked v ith tracer sircontun ftroed of niobium by TT« extraction. Usin^ th is

CW as r. food solution, an extraction and aovjral scrubs wort siuulatod batchvisc

using t 3 X HF)* scrub, a 1 # TOP • Deo Paso ex trac tan t, and a scrub/fjod/extrac-

tan t volume ra tio of 2/3/10. Tho resulting XhfS composition vas 0.23 M UKH. 0.20

M H3PO4 , 0,20 K HjSO , 3-6 H EWO3, 0.0^5 M K0IIO3. Unexpectedly, none of the

organic phaoos contained gaonaoctlvlty greater than tho Shonka background. Thuc9f a )thu zirconium distribution coeffic ien t, *n, vns less than 10

The above experiment vr.a repeated using a tvo-nonth old somplo of

current rw tal v tjto solution (&-3-WS), Again tho ocrub/fecd/cxtroctant rubrnt

ra tio vos 2/3/10, but both the foed end scrub vers acidified to * M BKO . Tho

effect of adding 0.0b M omentum fluosiU cete to both food and scrub was also1 \

observed. One extraction and onj scrub vore carried out using a colvunt and scrub

pro-equilibrated v ith respect to uranium and n i t r ic acid, Tho gross caaso

a c tiv it ie s of tho sovarol phases were determined v ith tho Shonka counter and

radiochemical essays vure made for zirconlun. Tho tabulated values, particularly

those for zirconium, oro uncertain due to tho very small activ ity remaining in

tho organic phase,

• • • • • • « • SM S SM • •e s e t t e e s s • s e e s • •e s e s s 1 e s s • » • » • • • • »e s e s e ees e e s e e s v #s e e e s s » 1 • e s s • ♦ e ss e ese e ese • • «• • • s s • see es**•+*+*> w ;

* .;’v ':'; »

* , I . I m u c *5°- W-16076

Tabio mixaDcarr;jtiiuTi3 or camwr nttai watts

s r n u r a ® w ot ib p

Orosa 0*■ » tircoaiun Gross Quanta tirconluB

rluoa ll catu eoncontrition, H 0 0.3k

Extraction, I* ?.J * U)*5 X> S 10**» > s 10 ' t 1.5 i 10'*

Scrub, 6.6 * 10*5 6 a 10’2 a 3.9 » 10*a

Over-a ll B.P. l.T « 105 1.2 * lO* >lo5 2 * 10^

• Only bacfcgr**^ a c tiv ity d e tec ted In tto organic phase.

With nddjd f iu o s U ic a te gro*& bet,t analyse* of the phases fro n the

scrub stop in d ica ted 7 .9 x 10* and 5 ,7 x 10* c t / a / a l (Ptui sh e lf BOO) in tho squooua

and organic phases, re sp ec tiv e ly , This corresponds to a d is tr ib u tio n r a t i o , E^,

of gross b o ta a c t iv i ty on the f i r s t scrub o f but 7 ,3 x 10-3. The f in a l organic

b e ta a c t iv i ty i s equivalent to cu . IT cz/vjvq, o f U ns compared to 66 ct/m /ng fo r

n a tu ra l u re n iu a . Thus cn e x tra c tio n and a sing le scrub on tvo-»>nth old CW

yielded a jro d u c t having a g ross b e ta a c tiv ity only 2 # th a t o f n a tu ra l uranium.

That theso decontam ination fac to rs arc h igher than those rep o rted

to date by GRUL nay ba dui to the fa c t th a t th3 TBF used hero ves vacuum A lai I l ia d

nnd th a t tiw d ilu e n t, Ooo Baoo, con tains vaallo r concentrations- of s ro n n ic s and

unsaturatvS than loos Vur6ol, Those poin ts v l i l bo in v estig a ted ra n h e r using

froah CW.

2 . Extraction Behavior of T rlcro sy l and Tr^puenyl Phosphates

In viev of the g rea t in te re s t in TBP as ar. o rtra c ta u t fo r uranium

end plutonium i t soewd o f in te r e s t to in v estig a te the behavior of re la te d com-

founds. T riphenyl phosphnto (TPP), a vhito c r /s ta lU r .) s o lid , and t r ic ro s y l

phosphate (TCP), a :o lo rlo ss v iscous liq u id , are tvo vhich oro av ailab le in

• i• • • • • • • • • •

« si* t• • • •see • • so• •• • •

« • • • « • • •

9 . 1, Kate*. W -I60T6

nn—nrclal quantities, the Uttar as « mixture of the oartho and n U form*.

Jobations of 20 mslgfct $ TBP • CCl and 20 rolmoo f TCP - CCI mare contacted

v llh a 0*2 M UKH, *) K 390 solullea Lad th* distribution of both urealwi cad

n itr ic ec?d into the organic phiearn mscaurod.. Subsaqwatly, the aqpftMt* pha»a«

tw o spited irith tracer Pu(n) end l i t distribution sua ajejur^d.

Table initt3t»auriQ« or tj(vi), w (rv}, aid wa3

ikto r» p : » tcp

Equal phase volucu con tact r.t roan tonperaturv; hqu**ia: 5 M WO3, 0 ,? K URB (except *, **)Organic*: 20^ ind icated phosphate in CCI4 (except ♦)

* In to 1% TBP - loo Beaci, in absence of u roa iua .

M In absence of uranium.

I t v i l l be noted th a t the e x tra c tio n of both u ran iua and plutonium

by TPP and TCP is lo ss than tha t by TBP by sev e ra l ordera of m agnitude. Tills nay

bo a t t r ib u te d to a to r ic h indrance, tho b asic oxygen aton of the phosphate ra d ic a l

being a ffe c tiv e ly sh ie ld ed fi*on the hoary olanatnt ions by the largo phenyl groups.

By conpcrlson, tho e x tra c tio n of n l t r ’c a c id by 7PT aid TCP is found to \>, r e la ­

t iv e ly higfcar and coaporoblo tc th a t by TBP. This night bo -xpected i f n i t r i c

a c id ex trac tio n Involves h y d r i n bend form ation, since nuch bonding would not

req u ire ms close approach to the phosph&to r a d ic a l by the n i t r a te ion .

TPP 7 .6 * 10-3 l . M * 10*3 3.6 1 10*2

TCP 9 .2 * TC*3 i .g a x 10*3 U , 10' ?

TBP 12.lt 10.3* 0.13**U/.3* 0.13**

B. I* Bcatoii -3?- 8W 160?*

» * i g g t a ^ i a . s r j H a m a s a r a a s g i L a ^ y ^ w ; a m(H. S. Bums, C, H. Bo la , R. Mathoson)

1 . 221 Building 5-6 Waste

PlutoalttB and gross beta scavenging of 221-5-6 were investigated

using plant batch #57 of th is waste which in it ia lly coatainod 6.0 x 10'^ /*g/cc fu

cad 0.U3 ac/ cc gross beta, vn* 1,25 M in HUO , and was vary lev in to ta l solid*

content. The standard soavongth procedure involved oUing W h ot scavenging

solution with 25 a l or waste followed by the addition of ca* 1.6 a l of 5 # BaOB

to 01 10. ‘fhc resulting slu rry stirred for eno hour, thou a 10 n l aliquot

woa taken for se ttling observation* cad a 6.5 n l aliquot for a 5-Binuto cen trifu ­

gation* centrifugate v ts oralyied for gross buta by direct evaporation and

for plutonlua by tho LeF procedure, the results arc g ven in Tabi* XI.

I t would appear fran those rosuits as v e il as free experience with

previous 221 5-6 samples (HW-1575*0 that tho m ute I t s e l f coatains enough basic

Insoluble Material to reduce ylutoniun to < 5 x I C '^ g / c c and to renew about

6qI of the beta ac tiv ity . Addition of noro scavenging agent doos not tierhwdly»

laprovo b e ta dccontaninfttion. With rospoct to plutonlun dorontaninat ion if should

bo pointed out that the tabulated values tn Table XI are subject to coatidercJblu

s ta t is t ic a l uncertainty since < 5 x lO^.Ag/cc Is c^iivolont to «. b c t/» with the

1 cc saaplos used for analyses. Ittpcnddblo dunonstration of lower concentrations,

o .g .. the Chalh Riser Confer ence tolerance valua of b xlO*^ .g /cc, awaits nodtfi

cation of tho LaT procedure which is now in progress.

R. H. Boaton -3 3 -T ablo XX

HW-16076

HWTOHIUK AID GROSS BETA SCAVKBGU® OP 221-5-6 WASTE

221-5-6 P la n t Batch #57I n i t i a l a c t iv i ty ; 6 ,0 x 10~3 s* g jc c Pu; 0 ,8 8 ^ c / c c g ro ss b o ta

C on trifugato_______________ Volunc B oductionScavenger P lu to n iu n d ro ss Bota C en tr ifu g ed S e t t le d• *

Ion Molar Cone, >*k/ cc x 10' O.P. y.. c /c c D.P. Was to S o l ’n . / p p t . Tiao, h r s . Waste S o l’n.APpt* « * • •

Mono addod 3 190 0.16 5 .5 110 IB 20• •• 42 20

• • *>♦♦♦ 10-2 1 ■»4oo 0,12 7 .6 35 0 .5 5« ** «# 5 \ 70 3* •• ♦ ♦ #0 1 ?<>♦♦♦ 10*3 4 170 0.14 6 .6 55 0 .5 7

23 8

?<>♦♦♦ ur* 1 £•400 0.14 6 .4 70 0 .5 8• * 19 10

C\i+*

<v13

2 300 O .lfl 4 .9 40 0 .5 867 12

Cu++

cr,13

2 300 0.16 5.5 55 0 .5 722 8

10-2 14 40 0.13 6.8 25 0 .5 420 6

C a " 10~2 6 100 0 . l4 6.0 25 0 .5 44 4

m : *CM13

1 ->hO0 0,12 7.5 20 0 .5 342 5

mmm

R. H. Boaton HW-16076-34-

2• 231 IcelatUn Building Va3t03 - Process and Laboratory

Plutonium scavenging studios wore al*o made on n. sample of 231

waste from process run #979 vhich initially contained 4.4 x 10‘4 .'-g/cc Pu, hnd a pH of 3.6, and was vary lov in toted solids content. Again, tho waste was

brought to a pH of ca^ 10 with NaOH follovng scuvnngor addition, tho resulting

slurry stirrod for one hour, and thjn centrifuged. Alpha analyseb of tho oontri

ugatoo indicated reduction of tho Pu concentration to *5 x lQ“?wg/cc following

scavenging with 1CT1* M or 10’2 M Fo+44, Cu+4, Ca*4 and La4*4 nitrates. Scavenging

with 10"1* M or 10*^ A tannic acid by adding Ca(0H>2 to pE 7.8 (»u3U5-C/R-2S?) also

lowered tho plutor.iun to < 5 x 10"> y*g/cc. By comparison, neutralization to pH

10 without added scavenger roducod tho plutonium only to 12 x 10"^ y.g/cc. Again,

low residual plutonium concontrations would not permit choice of tho most offoctirc

scavenging agont.

Similar studios with 10"1* M scavenging agents wore made on crunplo

#807 or 231 laboratory war.to vhich contained l.>0 x 10‘2 *«.g/cc plutonium raid had

a pH of ecu 2.0.

Table XXI

PLUTONIUM SCAVENGING PROM 231 LABORATORY WASTE

Plutonium_Scavenging Agent J S - j'n/cc, Centrifugate x 10" 0 SiEx

Hone added 7.8 2.6 6Fo(H03) 10 1.0 15Cu (1*0 3 ) 2 10 1.2 12Al(H0,), 8.9 4.7 3Ca(H03)2 11.3 2.1 7ladf03)3 10 1.4 11U02(H03)2 10 . 1.2 12Tannic acid 7.8 0.07 200

• • • • • •• • #• ♦ •• • • • •• 1 • • • •i« • ««

♦ t • * •

R. H. Beaton -35- HW-16076

Evidently tho tannic acid is noro offoctivo as a plutonium

scavenging agont thntn any of tho hydrous oxidos investigated. Tho decontamina­

tion achiovod by tho host of thoso oxides, vix.# Fo444, was invootigated as a

function of pH end found to bo a maximum at about pH 10 as in Table XXI. At pH

7, tho decontamination factor va3 2.9, at pH 12, 2.6.

Plutonium scavenging by tannic acid vaa investigated further as a

function of pH, scavenger concentration, and tho alkali used for neutralisation.

Table XXII

PLUTONIUM SCAVENGING FROM 231 LABORATORY V/4SSS WITH TAHKIC ACID

Tannic Acid ?u, ."g/cc x 10-5 in Contrifugeto Pu, 4?.J2L Molar Cone. TSXali: TOT" Ca(oHL N n ® CajOH)3

7.P 0 2.6 k.k 5.8 3.4r.e 10-6 3.1 3.9 4.8 3.87.8 10-5 2.0 3.7 7.5 4.17.8 io-1* - 0.07 - 2006 1°7 1.8 1.4 0.3 10.110 10-J <.0.05 *0.05 ...300 >30012 10*4 * 0.05 *0.05 *300 •=►300

Much the sano decontamination rosultc are obtained vlth aithor HaOH or CatOH^,

Residual plutonium can bo reduced to <5 * 10“ /*g/cc by 10"1* tannic acid in tho

pH range cat 8-12. Uny further investigation should include lovar tannic acid

concentrations at pH >8,

A comparison of tho Bottling ratos of 10"4 M tannic acid precipitated

by NaOH and Ca(OH)^ was made ou 100 ml samplos of 231 laboratory waste ;?4807. Tho » <*

slurries voro otirrod for five minutes aftor alkali addition to pH 7.8, thon

allevod to 6ottlc in 150 ml b3akors, Semples of supornato for plutonium analysis

voro withdrawn from tho top centimeter of the ca. 5 cm depth as r. function of timo.

• •

• •

• •

• •

• «

t •

IM. W W M

R . H. Boston

C O N F ID E N T IA L-36- HW-16076

%

Toblo XXIII

SETTLING RATS OF TAHNIC ACID SCAVEHGBRin 231 laboratory waste

Pu, a+rJcc x 10” ^ in Supornato Pu, D.F.T ina A lk a li: NaOH Ca(0H)o HaOH Ca QH}„

5 m 14 14 1.1 1.130 n 11 6.6 1 .4 2.31 h r 4 .5 3 .6 3.3 4.2h h r 1.6 1.2 9 .4 12.53 d 0 .15 0.06 1O0 250

Again, tho ro appoarc to be l i t t l e ch o ice botvoon NaOH and Ca(0il)2 . Tho s l ig h t ly

f a s te r s e t t l i n g r a t j achieved v l th CcfOHj^ i s probably moro th an o f f s e t by th o

disadvantage o f i t s m c h lower s o l u b i l i t y . Thus ouch la rg o r rongent volunoa would

bo ro q u irad fo r n e u t ra l iz a t io n w ith CafOHjj un lo s3 c o l id a l k a l i could bo u sed .

j \ $ > A ( h ■ / ,

F . W. Albaugh

FWAtevh

■%m

C O N F ID E N T IA L;U i lV

•• ••• •• • • • •• • •• •♦ • • •• • • • •• I ••• t

• • * * Ml I • • • n t f • • •

• • • •