Contract No.

W-7405-eng-26

CKET.IICRL TECRNOLOGY D I V I S I O N

C'nemical Development Section C

A. D. Ryon
E'. L. Daley
X. S. Lowrie

DATE ISSUED

ORE( riIDGE WiTIONfll; LABORATORY

Oak Eidge, Tennessee
Operated. by
UTII O N CMiBIDE C 0-WORAT! ION

IJ. S . f o r the
A'TOMIC ETu'PGY COI4i'4ISSION

3 4456 0286379 4
 -2-

The basis f o r design arid scaleup of mixer-settl-ers Par t'ne

Dapex s o l v e n t ex&raction process was determined by a wiii;
operatiails study in s c a l e model u n i t s . R a k c o n s t a n t s for
uranium e x t r a c t i o n involving s t z g e e f f i c i e n c y , phase r a t i o , and
residence t i m e are d i i - e c t l y proportional t o t h e cube root of
power i n p u t i n t ~ i cmixer. 'i'ypical mixing requirements for 90%
s t a g e e f f i c i e n c y a r e 30 ~ ~ $ I . O O Ogal axid 2 iiiin residence for
e x t r a c t i o n , and. 0,7 hp/1000 gal and 1.5 min f o r s t r i p p i n g . The
scaleup of geometrically sinLj.lar mixers i s based on constant,
s p e c i f i c power 5 x p - t . The P ~ O Vcapaeity of gravity s e t t l e r s i s
l i m i t e d by a d i s p e r s i o n bartd, which i n c r e a s e s e q o n e n t i a l l y with
f l o w r a t e , %he scaleup of s e t t l e r s i s based. on consJmnl; flaw
rate o f d i s p e r s e d phase per. u n i t se%-l;l.erarea and comstartt band
thickness. The nomjnal flow cadpacity (50% of f l o o d i n g ) of t'ne
d i s p e r s e d phase i s approximately 1 sm/rt' of s e t t l e r a r e a ,
Ernlllsions s o l v e n t entrainment a r e minimizes by c o n t r o l of
mixing t o forli]. solv~zzt-cantinaous d2,spersian.s Operating data
from two uranium m i l l s confirm tlie scalelip relations over a
r a n g e of flaw r a , t e s of 200-fold.for mixers and 1008-Yol-d f o r
seLtlers.
1.0 SUbrnRY 4
2 0
e INTRODUCTION 6
8

25
26
26
29

29
30
37
44
45
45
49

62
 A b a s i s f o r design of m i x e r - s e t t l e r s w a s obtained by 2 u n i t opern-
t i o n s study of s i n g l e m i x e r - s e t t l e r u n i t s Y'he v a r i a b l e s a f f e c t i n g s t a g e
ef'ficiency of t h e mixer and phase s e p a r z t i o n in t h e s e " i t l e r were success-
f u l l y c o r r e l a t e d i n s r m l l , 6-in. -dia, uni-ts . Sca,leup w a s d.emanstrzted i n
t,nree s i z e s and was confirmed by plant datzt shoving a n over-all scaleup
2.1

of throughput ca.paci.ty of 200-fold f o r mixers and 1000-fold f o r setC1.m-s.

WLxer. S'Landard 'oaff led-tar& mixers were used because t h e f l u i d

mechanics a r e well. defined,. and t h e power inpui; can be calculr_teri from
turbi.ne s i z e and speed and tile 3-iquid p r o p e r t i e s . The mi-xers were evzlu-
a t e d with b o t h batch and continuous flow t o determine t h e e f f e c t of mixing
on t h e r a t e of uranium extra,ction and s t r i p p i n g .

h ' q e r i a e n t a l l y , t h e r a t e of uranium e x t r a c t i o n i s f i r s t order w i t h

r e s p e c t t o t h e uraatum concentration i n the aqueous phase, The m.'w con-
s t a i l t , k., the f r a c t i o n of' aqueous
i s r e l a t c d t o ilie s t a g e e f f i c i e n c y , !i,
i n -themixer, 3 / V , and t h e contact Lime, t, by t h e equations

(I - E )
12, 1
Batch : ka = -In y z
Continuous: Ira = - 2
-R -1.
I - K V b

'The equations were conyirmed a t !1/0 phase r a t i o s of l t / l and 1/1 a d a t

c o n t a c t t iine s from 0.5 t o 5 .O mi ri (continuous flow). 'l'he values of t h e
ra'ce c o n s t m t were then used t o c o r r e l a t e the e f f e c t s of the mixing vari--
r b l e s and t o determine scaleup f a c t o r s e

Batch r a t e constants, a'lthoiigii c o n s i s t e n t l y g r e a t e r than those f o r

continuous flow, were u s e f u l f o r deieriniriing the relaiive e f f e c t s of vary--
a b l e s and f o r guiding t h e continuous-flaw s t u d i e s .

The e x t r a c t i o n r a t e constants Rre d i r e c t l y proportional to t h e cube

r o o t of power i n p u t over a range of 2.5 t o 2-20hp/i000 gal. DZIX f o r two
dif'ferent chemical systems invol-vimg d i f f e r e n c e s i n aqueous composition,
D2EHPA concentration,and phase r a b i o ( 4 / l and l/l) f i t on a sinzle curve,
i n d i c a t i n g that t h e power ciepencknce of t h e e x t r a c t i o n r a t e i s not
e f f e c t e d b j r t h e usual composition v a r i s t l o n s expected in m0s-L urmiurn-
m i l l feed liquors.

A t constant power i n p u t t h e rate constant i n c r e a s e d n e a r l y linearly

,
with decreased. turbi-ne-tank diameter r a t i o (D/T) being n e a r l y doubled at
1/6 over t h a t a t 2 / 3 . A DIT r a t i o of 1/3 i s conmionly used Tor mixing and
was s e l e c t e d a s a. standard for comparison o f d i f f e r e n t s i z e d mixers.
 The e x t r a c t i o n r a t e i n c r e a s e s with i n c r e a s e d temperature, being
doubled f o r a 15% rise. The d a t a show a good f i t i n t h e Arrhenius equa-
t i o n , g i v i n g a value f o r AH of 8-9 kcal/mole.

Scaleup data i n 6-, 12-, and 20-in.udia mixers show t h a t t h e e x t r a c -

t i o n r a t e c o n s t a n t a t constant s p e c i f i c power i n p u t and constant D/T i s
virtua1l.y independent of mixer s i z e f o r t h e d i f f e r e n t chemical systems,
phase r a t i o s , and power i n p u t s t e s t e d . Therefore t h e c r i t e r i a f o r design
of large mixers can be s e l e c t e d from data obtained i n s#Li mixers,
D i r e c t scaleup i s based on constant power i n p u t p e r u n i t volume of geo-
metrica3.ly s i m i l a r mixers. Confirmation of scaleuQ was obtained from t h e
performance of commercial mixers (36 i n . dia) i n t h e Dapex e i r c u i t of a
commercial uranium m i l l .

Scaleyp based on t h e r a t e constant allows a choice of a range of

combinations of power i n p u t , residence time, and stage e f f i c i e n c y t h a t
can be used as a b a s i s f o r design. The combination b e s t s u i t e d f o r a
p a r t i c u l a r p l a n t depends on t h e c o s t s of power and mixing equipment.
One such combination s e l e c t e d f o r plant design w a s a power i n p u t of
30 hp/lOOO g a l a d 2 min residence time, giving 90% s t a g e e f f i c i e n c y ,
E x t r a c t i o n r a t c s for vanadium(1V) and i r o n ( I I 1 ) are slower than t h e
rate f o r uranium. The values of t h e r a t e c o n s t a n t s a t the same mixing
power a r e 1.4 f o r uranium, 0.84 for vanadium, and 0.10 f o r i r o n .

T h e r a t e of uranium s t r i p p i n g by sodium carbonate i s s i g n i f i c a n t l y

g r e a t e r than f o r e x t r a c t i o n , and consequently it w a s not s o thoroughly
investigated. Stage e f f i c i e n c y w a s higher t h a n 90% a t a, power i n p u t of
0.7 hp/l.OOO g a l and 1.5 min res-idence time or a t 10 hp/lOOO g a l and 0.4
min. Exact scaleup data weye n o t determined, b u t p l a n t d a t a obeained i n
3- asld 4-ft mixers show n e a r l y ZOO$ s t a g e e f f i c i e n c y a t 8 power l e v e l of
5 t o 30 hp/lOOO g a l and a residence time of 2 t o 10 min.
S e t t l e r s . The r a t e of primary phase s e p a r a t i o n aetermines t h e flow
c a p a c i t y of g r a v i t y s e t t l e r s . I n most cases t h i s w a s l i m i t e d b y the r a t e
of coalescence of t h e d i s p e r s e d phase ;and n o t by t h e r a t e of s e t t l i n g of
drops to t h e i n t e r f a c e . I n both b a t c h and continuous-flow t e s t s t h e r a t e
of coalescence was l a r g e l y dependent on t h e s e t t l e r a r e a and n e a r l y inde-
pendent of t h e d i s p e r s i o n volume. Consequently t h e b e s t c o r r e l a t i o n of
phase s e p a r a t i o n i s based on t h e flow r a t e of d i s p e r s e d phase p e r u n i t
s e t t l e r area.

A t s t e a d y s t a t e with continuous flow a d i s t i n c t band of d i s p e r s i o n

e x i s t e d a t t h e i n t e r f a c e , t h e t h i c k n e s s of which i n c r e a s e d e x p o n e n t i a l l y
with flow r a t e . Nominal flow c a p a c i t y w a s a r b i t r a r i l y d e f i n e d as t h e
flow rat.e causing a 5-in. band which w a s about h a l f t h e flow r a t e causing
a 2-ft; band. The flow c a p a c i t y was v i r t u a l l y unaffected by mixing power
and t i m e , densitiy and pH of aqueous phase, phase r a t i o , or type of d i s p e r -
s i o n w i t h i n t h e ranges t e s t e d , which were s e l e c t e d p r i m z r i l y t o b r a c k e t
expected varZati.ons i n the a p p l i c a t i o n of t h e Dapex process to uranium
inLlling. The flow c a p a c i t y was wrked1.y i n c r e a s e d by i n c r e a s i n g t e q e r a -
t u r e , being doir'ulerl. i n g n h g from 1 5 .to 45OC.

Scaleup d a t a i n 0.5-, 1-*8-, a.nd jt.O-fi;-dia settl-ers show t h a t dis-

p e r s i o n 'tiii.ckfless i s independent of sett1.er s i z e a t t h e same flow r a t e
p e r u n i t a r e a . Therefore t h e nominal flotir c a p a c i t y expressed as f l o w
r a t e p e r u n i t a r e a of sinall models can be used direct1.y as a basts f o r
design of l a r g e setttler;;, The l i q u i d depth i n t h e settler i s de.termi.ned
mainly by t h e s e n s i t i v i t y - of t h e i n t e r f a c e c o n t r o l device, A depth of
2 ft i s s u f f i - c i e n t f o r simple gravity leg c o n t r o l . The use of nominal
flow capacity. al.3.ows a s a f e t y f a c t o r of 2 f o r f l o o d i n g of a 2-ft l i q u i d
depth. The nominal flow c a p a c i t y of t h e dispersed. phase ranged Trom 1.0
to 1.. 5 gpm/ft' i n d i f f e r e n t - s i z e settlers and f o r aqueous-continuous d i s -
p e r s i o n a t A/CI r a t i o s of 4/1_ 1/1 and f a r solvent-continuous d i s p e r -
s i o n s a t A/O of l/l and L/2. Scaleiup d a t a were confirmed. i n p l a n t set-
tlers of 7 and 16 f t d i a , which si-iowed consttint flow c a p a c i t y p e r u n i t
area over about a 1 C O O - f o l c l a r e a increase.

Entrainment of s o l v e n t i i i Lhe aqueous w a s c o n s i s t e n t l y less t h a n

0.2 g;al/b000 gal, f o r solvent-continuous d.ispersions a t A/O phase r a t i o s
of i/l and ,112 Enti-airunen'c, f o r aqueous-continuous mixing ranged fraln
0.2 t o 3.0 ga1/1.000 g a l , t n c r e a s i n g with i n c r e a s e d r a t i o of a,queous to
solvent. H i g h entraiilmcilt; wm reduced t o l e s s t h a n 0.2 ga1/1000 gal by
passing .the aqueous phase through a secondai-y settler desfgned f o r b w
turbulence with an aqueous resid.ence time of about 30 rnin.

Kmulsions were formed wl.t,h a number of p l a n t l e a c h l i q u o r s which

contained s:i.lic=i. rangi-ng froin 0.1 t o 2.5 g o f Si02 p e r l i t e r . The ernul-
s i o n s were an o i l - i n - ? a t e ? ? type and could be prevented eri.'cher by adding
c e r t a i n su rfac L m t s oi" by c o n t r o l l i n g the mixing fsr a solvent-continuous
d i s p e r s i o n . 'The l a t t e r j-s p r e f e r r e d because 5.t minimizes both emulsion
f o r m t i o n mid s o l v e n t entrainment vi-thout a f f e c t i n g s t a g e e f f i c i e n c y .

2 0 INTRODUC'l?ION

This r e p o r t suinmrizes t h e engineering stud3.es of mixer-set'iless for

the Dapex solvent, extrac%j.on. process. Mos-t of t h e results have been pub-
1i.shed i n m m t h l y progress reports 'The variables a f f e c t i n g s t a g e
efficiency-, phase separation; and- scaleup were measured t o provide a
b a s i s for design of p l a n t equipment. 'The work was d i r e c t e d tawart1 ap-
pll.cation o f a t h e process for recovery o f uranium from s u l f u r i c a c i d Leach
l i q u o r s i n uraniim mills. 'Design data g e n e r a l l y aye r e q u i r e d for any new
process, and i n this case it was p a r t i c u l a r l y t r u e because solvent extra,c-
tj.con techntqiies weri' novel t o t h e i r r a n i u m inill-ing i.jld.ustry.

Althoi-1.gh t h e i i x e r - s e t t l e r i s one of .the o l d e s t types of c o n t a c t o r s

used for liqui.d-!.iquid e x t r a c t i o n , t h e r e are r e l a L i v e l y few publl,shed
methods of scaleup,. Even more r a r e l y b.as t h e r e been any sttempt; t o
 -7-
verify the methods from the operational data of full-scale plants.
Results of previous studies of agitated vessels have suggested several
different methods of scaleup of mixers. Miller and Maxi3 in their study
of degree of mixing in unbaffled tanks suggested scaleup b use of con-
1
stant power input per unit mixer volume; Flylln and Treybal found that
stage efficiency was independent of mixer size at constant energy input
per unit volume of liquid processed; and Karr and Scheibel5 demonstrated
scaleup as a function of powers of agitator speed and tliatneter. For set-
tlers the suggested scaleup method has often been based on residence
tirne.6 Many patents have been granted for particular settler configura-
tions, 'out information on experimental demonstration of scaleup generally
has not been published.

Geography has precluded pilot plant operation with uranium ore liq-
uors at ORNL. Consequently engineering studies have been on a unit opera-
tions basis for evaluation of the principal variables affecting the rate
of extraction (and stripping) in the mixer and phase separation in the
settler. The effects of power input, phase ratio, type of dispersion,
and temperature on the uranium transfer rate were measured in baffled-
tank turbine-agitated mlxers. Both batch and continuous-flow mixing
techniques were used.

Phase separation was studied in gravity settlers t o determine the

flow capacity for primary phase break and residual entrainment. The ef-
fects of mixing power, type of dispersion, settles geometry, phase ratio,
and teqperature were evaluated. In addition, emulsion prevention with
certain ore leach liquors containing silica and/or ore slimes was
studied

Scaleup relations for both mixers and settlers were developed from
data obtained in three sizes of geometrically similar units. A check on
the scaleup relations was obtained from analysis of the equipment per-
formance data of two opera%ing uranium mills: Kerr-McGee Oil Industries,
Shiprock, N. M., and Climax Urmim Co., Grand Junction, Colo.

Acknowledgments. This report is a s m r y of work carried out over

several years by a number of people, The program was directed by H. M,
McLeod and K. B. Brown. Experimental work was done by H, F. Bauman,
J. R, Buchanan, J. P. Manneschmidt, R. R. Wiethaup, F. G. Kilpatrick,
C. E. Tipton, and K, Ladd.

The analyses required by the experiments were performed in the Y-12

section of the O a k Ridge National Laboratory Analytical Chemistry Division
under the direction of C. D. Susano.

Operational data of solvent extraction circuits in the uranium mills

were obtained with the excellent cooperation of the management and tech-
nical staff of Climax Uranium Company, Grand Junction, cob., and K e r r -
McGee Oil Industries, Inc., Shiprock, N. M.
 3.0 DAPliX PROCESS FLOS.JSacIJm

The solvent in the Dapex p r o ~ e s a ~ -( -F~i gl - 3.1) for recovery o f ura-

nium f r o m s u l f u r i c a c i d s o l u t i o n i s a dialkylphosphoric acid, t y p i c a l l y
d i ( 2-ethylliexy1)phosphos~iea c i d ( D 2 G L A ) , dissolved i n a kurosene-t4ype
.
a i l u e n t , u s u a l l y modified wjt'n Lributgrl phosphaic (TBP) Uranium i s
stripped from t h e s o l v e n t by sodiium or a m o n i m elzrbona-tc.

'The l i q u o r f e d t o t h e system i.s red.uced t o minimizz extraction ai:

f e r r i c ion. By appropriate ad.justmcnt of t h e e x t r a c t a n t concentration and
f l o w rates the u r a n i m i s e s s e n t h l l y conlpktely extracted from the liquor
i n 3-6 countercurrent s t a g e s , The uranium loading o f the solvent depends
or1 sei-ectian of process conditions, but w i t h 0,l M D2Uil'A it will u s u a l l y
be of t h e o r d e r of 4.5-7 g of TI308 per l i t e r . Zix-the carhonate s t r i p p i n g
cycle t h e uranium and any s-m1.1. ainounks of i m p u r t t i e s are removed i n 2-3
countercurrent sLages, g i v i n g a s o l u t i o n conLainirig 50-60 g of IJ 0 per
22
l i t e r . The e x t r a c t a n t , i n the farm of t h e :;odium s a l t 2 i s recyc e to t h e
e x t r a c t b n seetioil.

Uranium i s recovered fiorn t h e lo3Ad. s t r i p s d u t i n n 'DJ e s Labl-isherl

methods, one of which iflvolves d e s t r u c t i 011 of the earbonaLe w i t h s u l f u r i c
acid followed by a d d i t i o n of ammonia o r mgnPsia t o p r e c i p i t a t e i h c iira-
nium. P r i o r t o u r a n i m recovery the s t p i p solution can be f i l t e r e d Lo
r e m v e p r e c i p i t a t e d metal contami i i a n t s i f thei-P removal i s cl-esirtld.

U r m i u m I s extracted by c a t i o n exchange of uranyl ions and hydrogen

i o n s between t h e aqueous phzsc and the d i (2-ethylnexyl)phosphoric acid in
t h e solvent phase. The stoichtnmetry 02 the exchange r e a c t i o n i s

0 0

This equation i s over-silli_ulif~.l.ation and does riot t a k e t n t o account

polymerization 129'3 of t h e arp>aaophosphorie a c i d i i i t h e s o l v c n t or the
competitive e f f e c t s of uraniuru s u l f a t e csrrrpl.exPs i n t h e :queous phase e

F x p e r i m n t a l l y , the r a t e of uranium e x t r a c i i o n warJ Sound t o be first

order wiLn r e s p e c t t o tile uranium concentration i n tile :iqueous _nhc~seover
a wide ranse o f mixing conrlitions and uranium c o n c e n t r a t i o a s . If t h e TP-
a c t i o n i s treated its revzrsible 2nd f i r s t oraer i n both directions, t h e
k i n e t i c equation for b a t c h e x t r a c t i o n i s
 U NCLASSI Fl ED
ORNL-LR-DWG 47793

Leach Liquor
(Iron Reduced)
1.2 g ~3OdIiter

I
Precipi tote
Fe, AI, Ti, etc.;
Recycle to Leach
,up8 '""U1)

50-$5 g U308/liter*
-7 g
* 4.5 U3Odliter
Extract
Ura niurn Product

>75% U308

*
I
S t r i pp ing \o
I
I 1 (2-3 Stages)

.... ._ -I-
0.1 A?' Na Salt of
D2EHPA i n Kerosene
" O w i n g to transfer of water to the
+- 0.1 .%if TBP
Discard solvent, the aqueous volume de-
Raffinute creases during stripping which
(tO.OO5 g U308//iiter! raises the uranium concentration
above that expected from the
i n i t i a l flow volumes.

Fig. 3.1. Dapex process for uranium.

 -10-

S u b s t i t u t i n g i n eq. 1 and regrouping,

On i n t e g r a t i o n , when t = 0, C = ,C,

Le% k = kl + k_l and s u b s t i t u t e aV f o r A’; then

ka .:
(4)

If t h e s t a g e e f f i c i e n c y , E, i s defined by

t h e f i n a l form of t h e batch k i n e t i c equation i s

The e f f e c t i v e rate constant, ka, i s evaluated by sampling over a

p e r i o d of mixing t i m e a t constant power input; and phase r a t i o * The rate
constant i s direckly p r o p o r t i o n a l t o YIe sI.ope of t h e curve ob-t;ained by
-
p l o t t i n g I n (1 E ) YS t.

For continuous f l o w t h e kine-Lie equation derived from eq. 6 and khe

t h e o r y of s h o r t - c i r c u t t i n g presented by Maelllullin and W e b d 4 i s

Here t h e e f f e c t i v e r a t e constant; i s eva.lua-t;ed by operating a continuous-

flow mixer under constant mixing conditions and flow r a t e s and sampling
at’ s t e a d y state. The rate conatant i s c a l c u l a t e d from t h e measmx?d s t a g e
effici-ency, ~ x e volume, r and f l o u rates, The numerical values of %a are
very n e a r l y t h e same as those f a r t h e o v e r - a l l rmss t r a n s f e r c o e f f i c i e n t s
based on t h e aqueous phase. The l a t t e r are c a l c u l a t e d from Mui-phree s t a g e
e f f i c i e n c i e s and a r e not s o e a s i l y c a l c u l a t e d f o r batch mixing because
g r a p h i c a l integrixtion i s required.

‘PJOsystems (Table 4.1) were i n v e s t i g a t e d t o cover a range of chemi-

ca.1 compositions, solvent s t r e n g t h s and phase r a t i o s for ura.niwn recovery
from sulfuric a c i d leach l i q u o r s . System A i.s t y p i c a l of t h e conditions
 -11-

Table 4.1. Composition and P h y s i c a l P r o p e r t i e s

System A System B

Solvent

D i (2-ethylheyy1)phosphoric a c i d , M - 0.16 0.10

30
T r i b u t y l phosphate, $ / l i t e r 35
Dilueilt kerosene kerosene
Density, g / c c 0.83 0.82
Viscosity, centistokes 2.4 2.3

Aqueous f e e d

U, g / l i t e r 5 *2 1.2
Fe3fy & i t e r 0.52 0.33
AI, g l l i t e r 2.6 2.8
v (total), &iter 4.8 0.94
vS+, g/liter 1.4 0.94
SO^, g / l i t e r 89 51
pH 0.3 1.1
Density, g / c c 1*08 1.05
Viscosity, centistokes 1.14 1.06
I n t e r f a c i a l tension, dynes/crn 18,3 19.0
Phase r a t i o (A/O) 111 4/1

in rnills processing uranium-vanadium a r e s and system B i s t y p i c a l of eon-

d i t i o n s for processing of most uranium o r e s . The equilibrium d i s t r i b u t i o n
of uranium f o r both systems i s shown i n Fig. 4.1. The mixer was a b a f f l e d
tank a g i t a t e d with a f l a t - b l a d e d t u r b i n e i n t h e c e n t e r of t h e Liquid. The
l i q u i d depth was e q u a l t o t h e tank diameter. Three geometrically similar
mixers, 6-, 12-, and 20-in. d i a , were used (Fig. Lt.2)" The t o t a l power
i n p u t t o the mixer was c a l c u l a t e d from c o r r e l a t i o n s of t u r b i n e s i z e and
speed and l i q u i d p r a p e r t i e s as r e p o r t e d by Hushtonl5 and Laity:16

P = KpN3D5/g
The s p e c i f i c power i n p u t was c a l c u l a t e d i n horsepower per 1000 g a l qf
mixer c o n t e n t s from t h e t o t a l power and t o t a l l i q u i d volume of t h e mixer.

The mixers were operated with both b a t c h and continuous f l o w t o

study t h e e f f e c t s of power i n p u t , phase r a t i o , temperature, and type of
d i s p e r s i o n on t h e r a t e of uranium e x t r a c t i o n , Scaleup r e l a t i o n s were
determined batchwise i n 6-, 12-, a d 20-in.-dia mixers and with continuous
flow i n 6- and U-in.-dia mixers.
 -3- 2-

UNCLASSI FI ED
ORNL-LR-DWG 47803

0 0.4 0.8 1.2

U I N AOIJEOUS, g/liter
Fig. 4.1. Equilibrium distribution of uranium
between aqueous and organic phases.

fT7 DIMENSION RATIOS

D:Dp:L:W ~
OF TURBl NE

24:16:6:5

Fig. 4.2. Baffled tank mixers.

 -13-

4.1 Batch Mixing (See Table lO,l, Appendix)

The batch technique for determining the rate constant consisted of

mixing measured volumes of aqueous feed and solvent under constant mixing
conditions and sampling the mixture over a time sequence sufficient to
obtain equilibrium. The samples were dipped from the mixer without
interruption of mixing, and the separated phases were analyzed. The
-
effective rate constant was evaluated by plotting In (I E) vs t accord-
ing to eq. 6 . Typical curves (Fig. 4.3) are straight; lines to about 95$1
approach to equilibrium. The intercept at zero time is not In 1.0
because extraction continues during the time required for the phases to
separate after the sample is withdrawn from the mixer; therefore the
actual contact time is greater than the indicated sample time by At. The
observed time for phase separation of the samples is approximately 2nt.
However, the evaluation of the rate constant is not affected by At
-
because it is calculated from the slope of the curve Ln (1. E) vs t.

Effect of Type of Dispersion. With proper startup procedures either

an oil-in-water (aqueous continuous or a water-in-oil (organic con-
tinuous) type dispersion can be formed and maLntained at phase ratios
ranging from 10% to 80% dispersed phase without phase inversion. For
example, an oil-in-water t n e dispersion is obtained by starting the agi-
tator with only aqueous phase in the mixer and then adding the solvent.
Conversely, water-in-oil type dispersions are obtained by starting the
agitator with only solvent in the mixer. T h e tTJpe of dispersion is easily
determined by measuring the electrical resistance of the mixture, Since
the resistance o f the solvent is much higher than that of the aqueous
feed, when the organic phase is continuous the resistance of the disper-
sion is high, >lO,GOO ohms, and when the aqueous phase is continuous the
resistance is lov, 1-100 ohms.

The type of dispersion is important in practical solvent extraction

applications because of its ef€eet on phase separation rates and entrain-
ment. Consequently, the rate of uranium extraction wzs compared for both
aqueous continuous and organic continuous dispersions over' a range of
power inputs. The results show no significant effect of dispersion tTy-pe
on the rate of uranium extrzction:

Power, ka, rain,-' I)/T = 1/2

hp/lGGO gal Aq. Cont. Org. Cont.

5.9 0.88 0.79

20 1*35 1.29
67 2-18 2.18
220 2.68 2 .Og

Effect of Temperature. The effect of Lemperature on rate of extrac-

tion was investigated because of its practical importance in the plait
and also to aid in determining whether the rate-limiting step was
 l.C

-I
Lu

0.

0.0: .iL...l.... ~
I 1 ! I ....
0 0.4 0.8 1.2 1.6 2.
SAMPLING TIME, min
Fig. 4.3. Typical rote curves for botch mixing.
......... ~~

Aqueous Continuous
20 hp/lOOOgaI

Organic Continuous
5.9 hpjlOOO gal

3.0 3.2 3.4

RECIPROCAL TEMPERATURE, 1 03/"K

Fig. 4.4. Temperature dependence of uranium extraction rote.

 -15-

diffusion or ion exchange. In a series of organic-continuous tests in a

6-in.-aia mixer, wit'n a constant power input of 5.9 hp/lOOO gal and a
turbine speed of 400 rpm, k i varied from J.57 miri-l at C
'
5
l to 3.23 a t
55OC. T h e interfacial area per unit volume in two aqueous-continuous
tests, at 20 hp/lOOO gzl and 600 rpm, was nearly independent of tempera-
ture as calculated from Rodger'sl7 correlation: 46.9 cm"' at 20% and
45.2 cm"' at 49OC. Therefore the observed change in rzte of extraction
with temperature was not caused by the change in interfacial %rea but by
the change in the specific rate of transfer.

The p l o t (Fig. 4.4) of log ka vs reciprocr,l temperature is a straight

l i n e for the organic-continuous tests at 400 r p m , and the two points for
aqueous-continuous mixing at 600 rpm lie parallel to this line. The heat
of activation &,, was calculated from the data by means of the inte-
grated form of Asrhenius ' equation,
I \

The ma wcts 8950 cal/mole for the organic-continuous :ind ,7920 for the
aqueous-continuous tests. For diffusion processes AH8, is generally of
tine order of 5000 cal/m.ole, while for most chemical reactions it is
greater than 10,000 cal/niole; hence the temperature effect is inconclu-
sive 3,s to whether the rate-controlling step is an exchmge reaction or
diffusion.

Ef€'ect of Ratio of Turbine Diameter to Tank Diameter ( U / T ) , In

general, at constant power input, the efficiency of mixing of immiscible
1iqu.ids increases with decreasing ratio of turbine to tank diameter (D/T)
because of increasing turbulence.l9 The effect of D I T on uranium extrac-
tion was measured in a 12-in.-dia tank with 2-, 3-, 4-, 6-, and 8-in.
turbines at a constant power input of 20 hp/lOOO gal. Tne resulting rate
constants (Fig. 4.5) increased nearly linearly with decreasing turbine
diameter. The rate constant at D/T = 1/6 was 8bout double that at D/T =
2/3. The lower limit of D/T will be determined by the pumping rate of
the turbine, which is proportional to ND3. If the pumping rate in a con-
tinuous-flow mixer is too low, excessive short-circuithg can occur with
resultant loss of efficiency. To avoid this effect, a D/T value of 3-/3
was selected as a standard for study of other mixing variables.

Effect of Power Input. T h e effect of power input on the rate of

uranium extraction for both systems A and B (Table 4.1) was measured in
6-, L2-, and 20-in.-dia mixers with the power input varied from 2.5 to
220 hp per 1000 gal of mixer volume (Table 4.4). The rate constants, ka,
calculated at a D/T ratio of 1/3 f o r each test are plotted against power
input in Fig. 4.6. A single curve through all points is a straight line
with a alope of l/3> showing that ka is proportional to approximately the
cube rout of power Input. The good agreement of data obtained from dif-
ferent systems confirms the expected dependence of ka on phase ratio in
eq. 7. The agreement shows that the wide differences in chemical composi-
tion of the feed liquor and extraction agent concentration have virtually
no effect on the rate of uranium extr;zction.
 U NCLASSI FC ED
ORNL-LR-DWG 477Y4

0.1
................ I .....

0.3
..............1
0.5
, ...........
0.7
TURBl NE/TANK DIAMETER RATIO, D,/T
Fig. 4.5" EFfact i?f D/T ratio on rate of extrrrr:tiran i n batch inixer.

41 .................... -. -
.....-. ....... .................................

I
.-c
E
h
U
u
.Y

r
s
I-

-e
0.4 --1__..1.-.1.._1_... I 1 I I 1........ J.......I......I .....I....I....
I ..L
2 10 100 3 00
POWER INPUT, hp/1000 gal

ktch COnt i i l vous M i x e r Dio, iil.

9
System

B 6

*I
B
12

"1
B 20

Fig. 4.6. Correlation of rate constants w i t h power input i n batch and continuous
fiow experiments.
 A s shown i n Fig. 4,6, the rate constant a t constant power i n p u t i s
n e a r l y independent of t h e s i z e of geometrically s i m i l a r mixers over t h e
e n t i r e range of power i n p u t s t e s t e d . Thus scaleup of mixers can be based
simply on constant power i n p u t p e r u n i t volume of mixer contents.

E f f e c t of I n t e r f a c i a l Area. Although t h e term ka i s a l l that i s re-

quired f o r design and scaleup purposes, fundamentally it i s of i n t e r e s t t o
s e e how k alone v a r i e s w i t h t h e nrixing parameters, From ecific inter-
f a c i a l areas measured photographically by Rodger and TsicEgo for 50$ o i l -
in-water type d i s p e r s i o n s i n 6-in. -dia mixing v e s s e l s geometrically
s i m i l a r t o t h o s e used here, t h e values c a l c u l a t e d f o r k are v i r t u a l l y
constant and independent of t u r b i n e speed:

Turbine Speed, ka , "L1

rpm min-1
_I_
em
CL
em/min

350 0.88 16P

524 1.35 24P
787 2.18 365a
1170 2.68 520a

%ata obtained by e x t r a p o l a t i o n .

To explore further t h e value of k, t h e r a t e of u r z n i m e x t r a c t i o n

w a s measured i n a mixer where a f i x e d i n t e r f a c e was maintained between
t h e phases and each phase w a s a g i t a t e d w i t h s e p a r a t e t u r b i n e s . The rate
w a s determined a t t u r b i n e speeds of 30 and 60 rpm and ka was c a l c u l a t e d
from a p l o t of la (1-E) vs sample t i m e (eq. 6 ) . The data f i t on a straight
l i n e going through t h e o r i g i n , expected. The value of ka was independ-
e n t of t u r b i n e speed, 1.95 x' '01 min'l a t 30 rpm and 2.0'7 x lon4 a t
60 rprn, The area of t h e i n t e r f a c e w a s 186 em2, t h e t o t a l volume was
5 l i t e r s , and t h e s p e c i f i c i n t e r f a c i a l a r e a w a s 0,0372 emm1. Thc calcu-
l a t e d value of k w a s 5.40 x 10-3 cm/min, which agrees w i t h t h e value of k
obtained w i t h t u r b u l e n t mixing a t a 4000-fold g r e a t e r s p e c i f i c area,
160 em-'.
4.2 Continuous-flow Mixing (Table 20.2, Appendix)

The kinetics of uranium extraction were s t u d i e d i n 6- and U-in.-dia

mixers a t flow rates ranging from 0,15 t o 5 (gpa i n two chemical systems
(Table 4.1). The s t a g e e f f i c i e n c y w a s c a l c u l a t e d by eq. 5 from t h e
eqgilibrium curves and e f f l u e n t samples. The e x t r a c t i o n rate constant
was c a l c u l a t e d from eq. 7.

The equipment used i n continuous-flow t e s t s i s shown i n Fig. 4.7.

The aqueous feed and the s o l v e n t were prepared i n l a r g e batches and
s t o r e d i n head t a n k a . Each phase was pumped by a metering pump t o t h c
mixer, The phases e n t e r e d through a concentric entrance t o minimize pre-
mixing. The mixed phases overflowed from t h e mixer t o a c a t c h tank,
 U N CLA SS I FI E D
0R NL - LR- DWG 47799

Fig. 4.7. Equipment for continuous-flow mixing.

0 ' I I I I
0 40 80
EFFIClfNCY, 90, BASED O N FRITTED TEFLON SAMPLE

Fig. 4.8. Comparison of sampling methods (system 5),

 -19-
where t h e phases were separated md measured after each r%n. The s o l v e n t
w a s s t r i p p e d w i t h sodium carbonate and w a s a c i d i f i e d w i t h s u l f u r i c a c i d
before re-use.

Sampling. The mixer contents were sampled a t s t e a d y state, a mini-

mum of t e n volume changes being allowed f o r s t e a d y s t a t e t o be reached.
Samples of t h e d i s p e r s e d phase were t h e b e s t measure of t h e mixer con-
t e n t s , t h e s e being t a k e n through f r i t t e d Teflon with aqueous-continuous
d i s p e r s i o n s and through coarse f r i t t e d g l a s s with organic-continuous d i s -
persions. Samples of t h e mixed-phase e f f l u e n t from t h e mixer do not give
r e p r e s e n t a t i v e data on t h e c x t r a c t i o n i n t h e mixer because e x t r a c t i o n
continues while t h e phases are separating. iJith t h e p r e f e r e n t i a l l y wetted
f i l t e r s , c o n t r o l l i n g t h e head across t h e f i l t e r a t 3-4 i n . H20 m d e it
p o s s i b l e t o o b t a i n i n about 2 min a 15-ml sample of one phase containing
v i r t u a l l y none of t h e other. It w a s d i f f i c u l t t o o b t a i n only one phase
a t high power i n p u t or a t low phase r a t i o of d i s p e r s e d phases because of
t h e small drop s i z e of t h e d i s p e r s e d phase. Although material balances
were poor with t h e f i l t e r e d samples, w i t h both types of d i s p e r s i o n t h e y
i n d i c a t e d less uranium t r a n s f e r e n c e t o t h e s o l v e n t t h a n d i d mixed-phase
samples (Table 4.2).

Table 4.2. Comparison of Sampl-ing Methods

Uranium Concentration, g / l i t e r
Aqueous Organic
Calc from
RUn Fritted Eff luent Fritted Fritted Effluent
No. GI n ss Stream Teflon Glass Stream

Aqueous Continuous

573 3.6 3*2 0.84 1.9 203

574 2.5 1.9 1.6 2,A 3.4
575 2.1 1.3 2.4 3.2 4.0
Organic Continuous

576 4.7 3.2 1.2 2.7

581 3.8 1.3 1.7 4.2

Both Teflon and glass f i l t e r s were t e s t e d w i t h both types of d i s p e r -

sion. Under aqueous-contimuous conditions t h e uranium concentration of
t h e solrrent c a l c u l a t e d from a f r i t t e d - g l a s s sample of t'ne aqueous phase
w a s c o n s i s t e n t l y higher than t h e concentration measured i.n t h e s o l v e n t
sample taken through Teflon. It i s not p o s s i b l e for t h e s o l v e n t t o l o s e
uranium as it i s f i l t e r e d through t h e f r i t t e d Teflon; and t h e measure&
u r a i i i m concentration i n t h e s o l v e n t t h e r e f o r e cannot be too low, The
other p o s s i b i l i t y i s t h a t t h e c a l c u l a t e d value i s t o o high, which would
 -20-

be t h e case if f u r t h e r e x t r a c t i o n of uranium occurred while t h e aqueous

sample w a s being taken with t h e f r i t t e d glass. S i m i l a r l y , f o r solvent-
conti.nuous d i s p e r s i o n t h e value c a l c u l a t e d on. t h e solvent; from the aqueous
f r i t t e d g l a s s sample i s less than t h e value measured i n t h e f r i t t e d Teflon
s o l v e n t sample. The e x t r a c t i o n based on t h e e f f l u e n t sample, wl?,i.ch ap-
proximates t h e total. e f f i c i e n c y of a s i n g l e r a i x c r - s e t t l e r s t a g e , d i f f e r s
most from t h e efftci-ency based on the f r i t t e d 'T'efl-on sample when t h e r e s i -
dence time i n t h e mixer i s s i i ~ l l (Fig, . 4.8). 'This i s because t h e c o n t a c t
time during phase s e p r a t i o n i s constant and t h e r e f o r e t h e p r o p o r t i o n of
t h e extxaction t h a t occurs during pbase s e p a r a t i o n i s g r e a t e s t a t low
residence time i n t h e mixer.

E f f e c t o f Residence Time on Kate Constants. Equation 7 p r e d i c t s that

t h e rate constant, Ira, w i l l _ be independent o f residence time. D c t a ob-
t a i n e d with t h e G-in.-dia mixer a t t o t a l ;low rri,tes ranging froin 0.15 t o
5.0 e r n showed no systematic change i n ka f o r residence t i r n - s voryinq from
0.17 t o 4.8 min at differ2tl-t l e v e l s of gobwc i n p u t ,
E f f e c t or Eoirer h p u t . The r a t e constants were c o r r e l a t e d with power
i n y r t f o r both systems 4, =ind R i n 6- and 12-in. mixers ( F i s . )!.6,curve b ) .
The average vzlue f o r ka at various resi.denc:: times W;LS used ( T z b l e 4.3).
The D/T r a t i o w a s l / 2 i n t h e 6-in.-dia mixer and 1/3 i n t h e 1 2 - i n - - d i a
mixer. I n order t o cofnpnre t h e dzta at a cons1;an.t D/Y r a t i o , t h e r a t e
c o n s t a n t s for 6-in.-dia mixers were c a l c u l a t e d a t D/T: = l/3, using t h e
curve ( F i g . I!.5) showing t h e D/T e f f e c - t f o r 'uatch mixing.

The slope of curve b i n Fig. 4.6 i s a-nout l/3, showing iiiat the rate
constarit i s d i r e c t l y p r o p o r t i o n a l t o t h e cube rooi of power iliput, I n
t h e curve are included d2iz. obtained i n r o u t j n e npew.tion of p i e n t - s i z e
mixers i n t h e Dapex c x t r z c t i o n circu3.t a t C l i m x Uraniwn Co. Grarrd ,
Sunctj-on, Colo. ( d e t a i l e d d a t a ir, 'i'nble 8.1). Good agreement of data
from 6-, 12-, and 36-in.-din mixers ShQFas t h e independence of r a t e w i t h
respect t o mixer s i z e .

E f f e c t o f Phase 3ntio. l?ate constants are s l i g h t l y g r e a t e r for

Systeui A t h a n f o r system B. The two sy-s.teins d i f f e r i n uranium concentra-
t i o n , pH, D2EKE-A concelitration, and phase r a t i o . I n order t o d e f i n e the
e f f e c t of on.ly phese r a t i o o n r a t e of extract.i.on, one s e r i e s of r u n s was
.made w i t h system B simulating so.lvent r e c y c l e s o t h a t t h e phase r a t i o i n
t h e rnri.xes was l/1 i.nstend of t h e normal ratio ( i l / O ) of 4/1, The mixing
w a s c o n t r o l l e d t o maintain t h e sol.vcnt phase continuous. 'The r a t e con-
stctnts agreed very c l o s e l y at low power input, bul; a t high power i n p u t
were g r e a t e r a t a phase r a t i o of 3./1. than a t 4 / l ( T a b l e 4.4). Most of
t h e d i f f e r e n c e i s probably caused b y - a change i n t h e s p e c i f i c i n t e r f a c i a l
are,?. ,%xtrapolat.i.onof i n t e r f z c i a l a r e a data r e p o r t e d by Vermeulen21
shows t h a t t h e value of "a" should be about, 40% g r e a t e r a t a piizse ratio
of 1/1 than a t 4/l.

The stage e f f i c i e n c i e s were m z r l y independent of phnse r a t i o a t

c o n s t a n t aqueous flow r a t e b u t not a t consta,iit residence time, which i s
p r e d i c t e d by eq. 7. L'his .is of p r a c t i c a l inxportarice t o o p e r a t i n g p l z n t s ; ;
f o r exam@e, i f t h e mixers G J Q T ~designei! f o r a phase r a t i o of 4/L
 Table 4,3. Effect of Residence Time on Extraction Rate Constant

Residence
Time, Continuous

--
Svstem A
-.
~ ~~

0.37 Aqueous 0.31 0.78 1.50 3.09

0-37 Organic 0.23 0.28 0.70
1.40 --
1.50
2.25
-
0.82 Organic 0.86 2.02
0.65
-
I

1.5 Organic 1.10 1.51 1.51

0.66
1.5
1.5
Organic"
Aqueous"
0.49
- 0.83
1.13
1.40 L
1.55
1.60 -
1

avg a 0.34 0.68 1.21 1.77 1.93 1.88 I

Iv
P
I

System B
0.17 Aqueous 0.30 0-64 1.36 2.09 2.69
0.37 Aqueous 0.41 0.69 1.25 1.58 2*06
1.5 Aqueous 0.54 0.81 0.98 1.33 1.74
2.5 Aqueous 0.53 0.75 0.89 1.15 1.75
0,74 1.15 2.15
4.8
avg . Aqueous
Aqueous
0.43
0.44
0.59
0.70 1.04 1.46 2.08

Standard
deviation,
5 of avg. 21 12 24 26 18

&Uranium concentration i n aqueous feed was 1.7 g / l i % e r .

 Table 4.4. E f f e c t of Phase Hatio on E x t r a c t i o n a t Various
Aqueous Flov Rates and Residence Times
_L P
~

2.5 43.2 56.3 53.9 0.'13 Oe42 0.39

5.9 53.7 65.P G,O 0.65 0.60 0.64
20 5803 68.6 76.2 0.78 0,7l 1-06
67 65.1 74.1 84.5 1.06 0.92 1- 81
220 71-2 61.3 85.4 1.39 1.40 2.11

*Based on samples of dispersed phase taken with frit,Led samplers.

and subsequently it vas necessary t o operate solveat-continuous with

r e c y c l e s o Ynat t h e phase r a t i o i n t h e mixer was 1/1 to prevent emulsions
( s e e See. 7. I, p .30 ), t h e s h g e ei"fi.ciency would not be s i g r i -fi.ca:ntly d i f -
f e r e n t at the same aqueous Lhroughput .
4.3 C o r r e l a t i o n of Batch and Contiriuous Data

The agreement between t h e rat:? constants f u r batch and contihuous

flow i s c l o s e enough t o warrant t h e use of t h e batch technique 'io scout a
new system because of its r e l a t i v e s i m p l i c i t y . The r a t e of urani-im ex-
t r a c t i o n i s described by t h e rate constants c a l c u l a t e d from eq. 6 for
batch mixi.ng and ea_. 7 f o r continuous flow. Rssumi-ng t h a t a homogeneous
d i s p e r s i o n i s formed i n t h e mixer and t h e i n t e r f a c i a l arm 3.s the same
f o r batch and. continuous mi.xing, t h e r a t e constants should be equal a t
t h e same po?.rer i n p x t . The slope of t h e average batch r a t e CII.I"VP: j.s vir-
t u a l l y t'ne same 3,s t h a t for continuous flow, showtng t h e same dependence
on pover i n p u t and independence of mixer s i z e and chemical system, Th.e
batch r a t e constants a r e c o n s i s t e n t l y g r e a t e r t h a n those f o r continuous
flow, and t h e reason f o r the discrepancy i s not; known. The most probable
causes are t h e method of sampling snd d i f f e r e n c e s i n i n t e r f a c i a l a r e a
between batch and conLinuous mixing. A s pointed out i n t h e sa1np.l.lng
s e c t i o n , s e v e r a l d i f f e r e n t methods were used f o r t h e coiitinuous flow
t e s t s and the method s e l e c t e d was t o sample t h e dispersed phase because
it was found t o be f a r t h e s t from equilibrium. I f t h e sample of .the con-
tinuous phase i s used, t h e [email protected] batch and continuous mixing
i s good. However, t h i s may be only f o r t u i t o u s . There are no publ.isiied
data f o r comparison of i n t e r f a c i a l a r e a f o r continuous flow with batch
mixing; consequently it i s not p o s s i b l e t o check t h i s as an explanstion
f o r t h e Lower r a t e constants with conti.nuous-flow mi.xing.
 -23-

4.4 Scaleup of Mixers

Both b a t c h and continuous-flow mixing t e s t s show t h a t t h e r a t e con-

s t a n t for uranium e x t r a c t i o n i s independent of mixer diameter a t constant
s p e c i f i c power i n p u t and D/T r a t i o . This i s t h e b a s i s f o r d i r e c t scaleup
of geometrically s i m i l a r mixers.

The f i r s t s t e p of scaleup i s t o s e l e c t t h e combination of power i n p u t

xnd residence time r e q u i r e d t o give t h e d e s i r e d stage e f f i c i e n c y accord-
ing t o eq. 7 i n t'ne s c a l e model mixer. Next, t h e volume of t h e l a r g e
scale mixer i s c a l c u l a t e d from t h e p l a n t flow r a t e s t o o b t a i n t h e r e q u i r e d
residence t i m ? . The t o t a l power input t o t h e mixer i s c a l c u l a t e d from
t h e volume a d t h e required s p e c i f i c power i n p u t . The mixer diameter and
t u r b i n e diameter are f i x e d by geometric s i m i l i t u d e . F i n a l l y , t h e t u r b i n e
speed i s c a l c u l a t e d from t h e t o t a l power t u r b i n e diameter from l;he
power equation, P = KpN3D5/g. The parameters and scaleup method are sum-
marized i n Table 4.5.

Table 4.5. Scaleup of Mixers

Parameter S m a l l Hodel Large S i z e

Flow r a t e Q1 Q2
S p e c i f i c power input P l h "Z/VZ = PX/Vl
Residence time t1 tr-i = tl

Mixer volume

T o t a l power

Mixer diameter

5.0 KINZTICS OF VANADIUM AND IRON EXTINCTION

The r a t e s of e x t r a c t i o n of vanadium(IV) and i r o n ( l I 1 ) were surveyed
i n batch t e s t s w i t h 6- and l2-in.-dia mixers. The conditions were simi-
lar t o those encountered i n a p p l i c a t i o n of t h e Dapex process f o r recovery
of vanadium. The s o l v e n t v a s 0.24 M di(2-ethylhexy1)phosphoric r x i d i n
kerosene containing 50 g of t r i b u t y i p h o s p h a t e p e r l i t e r and t h e composi-
t i o n of the aqueous f e e d i n grams p e r l i t e r , was 0.9 V ( I V ) , 0.2 Fe(III),
3.0 Al, 50 504, and 1.9 Pol, a t pH 1.8. The r A t c s of vanadium and i r o n
 -2 4-
e x t r a c t i o n were rneasuretl si multaneously as a func Lion of power i n p u t a t
A/O phise r a t i o s of 4/1 and 1/l. 'The rate const2irlts, ka9 were evzluated
i n the smic way as described. f o r uranium i n S e c . 4.0. 'The test data are
shown i i i Table 10.3 (ilppcndix) and t h e r a t e c o n s t a n t s a r e correlated v i t h
power i n p u t i n Fig. 5.1,

-
-I
I
.-cE
U
Y

00.05 ' -L-LJ-..

-......_._.I. ! . . . l . . . l . . J . - L d
2 10 100
POWER I NPUT, hp/1000 gal
-in.-dia m i x e r r A/O = 1/1
0 6-in.-dia mixer, A/O = 4/1
12-in.-dia mixer, A/O = $/I

Fig. 5.1. Batch extraction rate constants far uranium, vanadium, and iron.
 -25-

The slopes of t h e curves (Fig. 5.1) are v e r y similar for uraniw.,

vansdium, and i r o n , showing t h a t t h e r a t e c o n s t a n t f o r each i s dependent
on t h e cube r o o t of power i n p u t f o r both 6- and 12-in.-dia mixers. The
r e l z t i v e magnitu.de o f t h e r a t e c o n s t a n t s a t c o n s t a n t power shows that t h e
r a t e of vmadium e x t r a c t i o n i s lower t h a n t h n t of uranium and t h a t t h e
i r o n rate i s about one o r d e r of magnitude lower. For example, a t a power
i n p u t of 20 h.p/lOOO gal, t h e values of t h e rate c o n s t a n t s a r e 1.4 f o r
urmxiuul, 0.84 f o r vanadium, and 0.10 f o r i r o n .

D i r e c t comparison of t h e r a t e constcants a t an A/O phase r a t i o of 1/1

vs 4/1 shows t h a t t h e rates of vanadium a i d i r o n e x t r a c t i o n are about 25%
g r e a t e r at 1/1. The rates were n o t a f f e c t e d by t h e type of d i s p e r s i o n ,
being t'ne same f o r both oil-in-water and w a t e r - i n - o i l t y p e d i s p e r s i o n s a t
a phase r a t i o of l/1. These r e s u l t s are c o n s i s t e n t w i t h t h o s e found f o r
uranium e x t r a c t i o n .

T'ne b a t c h values of t h e rate c o n s t a n t s can be used t o c a l c u l a t e t h e

s t a g e e f f i c i e n c y of t h e mixer operated w i t h continuous flow by using
eq. 6 . For example, with mixing c o n d i t i o n s for good uranium e x t r a c t i o n ,
30 h p / l O O O g a l a n d 2 min r e s i d e n c e t i m e a t a phase r a t i o of 1/1, t h e c a l -
c u l a t e d s t a g e e f f i c i e n c y i s 87% f o r uranium, 79% for vanadium, ,uld 31%
€or i r o n ,

6.0 KINETICS OF URANIUM S'ICfiIPPING WITH SODIUM CARBONATE

The rate of uranium s t r i p p i n g from t h e s o l v e n t with s o l u t i o n s o€
sodium carbonate w a s determined i n a 6-in,-dia, mixer by b o t h t h e b a t c h
technique and continuous flow. The rate of s t r i p p i n g i s s i g n i f i c a n t l y
g r e a t e r t h a n t h e r a t e of e x t r a c t i o n ; t h e r e f o r e o n l y a s u r v e y s t u d y w a s
made. Batch data showed that t h e s a t e of s t r l p p i n g i n c r e a s e s w i t h i n -
creased excess sodium carbonate and i n c r e a s e d power i n p u t , Continuous-
flow t e s t s showed t h a t g r e a t e r t h a n go$ s t a g e e f f i c i e n c y w a s a t t a i n e d
over a range of uranium c o n c e n t r a t i o n s s i m u l a t i n g two c o u n t e r c u r r e n t
s t r i p p i n g stages.

The s o l v e n t w a s 0.16 M di(2-ethylhexy1)phosphoric a c i d and 35 g of

I

'TBP p e r l i t e r i n kerosene. It w a s loaded w i t h uranium by c o n t a c t i n g w i t h

a s y n t h e t i c l e a c h s o l u t i o n c o n t a i n i n g uranium, i r o n , aluminum, t e t r a v a l e n t
vanadium, phosphate, and s u l f a t e . The s t r i p p i n g agent w a s aqueous sodium
carbonate.* The O/A phase r a t i o was c o n s t a n t a t 5/1, and t h e concentra-
t i o n of sodium carbonate was a d j u s t e d t o g i v e t h e desired excess. The
mixing w a s c o n t r o l l e d t o produce solvent-continuous d i s p e r s i o n s and the
temperature was 24 t o 3 0 0 ~ .
*The s t o i c h i o m e t r i c requirements w e r e assumed t o be 3 moles of N ~ Q C Op~e r
mole of u r a n i u m p l u s 0.5 mole p e r mle of f r e e D2EEPA.
6.1 Batch S t r i p p i n g
The batch technique d-escribed f o r uranium extimetion (See. 4.1,
p. 13) w a s used t o study t h e range of v a r i a b l e s a f f e c t i n g s t r i p p i n g . The
f i r s t - o r d e r k i n e t i c equation

-In (1 - E)--
K 1
V t

w a s used where stage e f f i c i e n c y , E, was c a l c u l a t e d from t h e uranium con-

c e n t r a t i o n s I n t h e solvent and R/V w a s t h e f r a c t i o n of so1ven.t i n t h e
mixer. The r a t e constant w a s evaluated from t h e s l o p e of t h e curve ob-
t a i n e d by p l o t t i n g L i (1 - h;) vs t . 111 s e v e r a l cases r a t e curves were
not well-defined because the r a t e w a s s o high t h a t equilibrium was
reached i n Less t h a n 20 see.

E f f e c t of Excess Sodium Carbonate. The e f f e c t of excess sodium car-

bonate on t h e s t r i p p i n g r a t e was measured a t consLant mixing pow~zr
(420 rpm, 6 hp/l000 g a l ) and constant Q/A phase r a t i o , fs/l. Tlne amount
of excess carbonate w a s varted by a d j u s t i n g t h e concentration of t h e
aqueous s o l u t i o n . The value of ka f o r uranium s t r i p p i n g irzcreased from
3.5 t o 9.3 min-1 as t h e excess sodium carbonate w a s increased from 1-9 t o
55$ (Table 6.1, Fig. 6.1-1.
For p r a c t i c a l a p p l i c a t i o n the amount of excess sodium carbonate
should be kept l o w t o minimize chemical c o s t . Therefore t h e r a t e af
s t r i p p i n g a t 19% excess probably i s t y p i c a l f o r a c t u a l p l a n t o p e r a t i o n .
Comparison of s t r i p p i n g r a t e with e x t r a c t i o n shows t h a t stripping i s
about t h r e e times f a s t e r a t t h e same power i n p u t ,

E f f e c t of Power Input. The e f f e c t of power i n p u t on t h e r a t e of

s t r i p p i n g w a s measured a t c o n s t a n t O/A phase r a t i o , 5/L, wit'h. 55$ excess
oodium carbonate. The r a t e constant i n c r e a s e d about t h r e e f o l d ( 9.3 to
24 min-l) when t h e power w a s t r i p l e d (6 t o 19 hp/LOOO g a l ) (Table 6.1) e

T'ne r a t e w a s t o o l a r g e t o be measured a t t h e next higher power l e v e l

t e s t e d (63 hp/lOOO g a l ) .

6.2 Continuous Flow Mixing

G r e a t e r t h a n 90% s t r i p p i n g s t a g e e f f i c i e n c y was read.ily a t t a i n e d i n

both s t a g e s of a two-stage c i r c u i t with t h e 6-in.-dia mixer. A t a r e s i -
dence time of L.5 min tine efficiency was g r e a t e r than 90% a t t h e l o w e s t
power iiiput t e s t e d , 0.7 hp/lOOO gal; a t a residence time of 0.38 min t h e
power r e q u i r e d for 90% e f f l c i e n e y WES about 10 hp/lOOO g a l (Table 6.2).

A two-stage s t r i p p i n g c i r c u i t w a s simulated by f i r s t c o n t a c t i n g t h e
loaded s o l v e n t w i t h sodium carbonate and sdosequently contacting t h e par-
t i a l l y s t r i p p e d s o l v e n t with f r e s h sodium carbonate. The solvent w a s t h e
same as t h a t used f o r tine b a t c h t e s t s , The concentration of t h e s t r i p p i n g
- a.
s o l u t i o n w a s 1 M Na2CO and .the phase r a t i o was a d j u s t e d so t h a t 45$ ex-
c e s s carbonate was use The mixer was t h e 6-in.-dia baffled tank shown
 Table 6.1. E f f e c t of Carbonate Excess and Pover Input on S t r i p p i n g Rate

Mixer: 6 i n . d i a with 3-in. turbine

Solvent: 0.16 M DEKPA, 35 g of TBP p e r l i t e r
Phase r a t i o , O/A? 5/1

Power
Input, Na2C03 N a 2 C O 3 Uranium Concentration i n Solvent, g / l i t e r
Run hp/lOOO Excess, Conc , ka ,
No. gal 46 -K 0 sec 10 sec 20 sec 30 sec 60 sec 120 sec 240 sec 480 sec min"l
I
6
11 6 19 0.73 5.2 2.9 1.5 0.60 0.37 0.37 0.38 0.36 3.5 4
:

9 6 32 0.81 5.2 2.3 0.56 0.31 0.36 0.33 0.33 0.33 4.7
7 6 41 0.87 5.2 1.6 0.33 0.30 0.33 0.32 0.32 0.32 6.8

1 6 55 0.95 5.2 1.1 0.32 0.29 0.30 0.31 0.31 0.31 9.3
 IC

2 -....I-I _
_
_
- __
10 30 50
EXCESS SODlUM CARBONATE, %

Fig, 6.1, Effect of excess sodium carbonate on

uranium stripping mate.

Table 6.2- Stage E f f i c i e n c y f o r Uranium Stripping

Y i t h Sodium Carbonate

'I?urisi ne Power
Speed, Input, 0.38 mi

200 0*7 .
% . - 93 94.
300
400 2.2 73 96 98 99
600
5.3
1-8
82 98 99 99
35 98 99 99
900 60 98 98 100 s
 -29-

i n Fig. 4.2, T'ne s t a g e e f f i c i e n c y w a s c a l c u l a t e d from t h e a n a l y s i s of

t h e organic e f f l x e n t stretun. The o p e r a t i n g data a r e given i n Table 10.4,
Appendix.

6.3 scdeup

EcaLeup of mixers f o r uranium s t r i p p i n g has been assumed. t o follow

t h e sane r e l a t i o n s doveloped for e x t r a c t i o n , i . e . eeornetric s i m i l i t u d e
w i t h constant power i n p u t and residence time. Limited confirmation of
scaleup i s shown by p l a n t data (Table 6.3), although t h e p l a n t mixers
were t h e same s i z e as those i n t h e e x t r a c t i o n c i r c u i t for s i m p l i c i t y of
o p e r a t i o n and maintenance. Consequently, t h e p l a n t mixers are over-
designed w i t h r e s p e c t t o requirements f o r uranium s t r i p p i n g . Hotfever,
t h e p l a n t d a t a do show t h a t n e w l y loo$ s t a g e e f f i c i e n c y 'ms obtained a t
power i n p u t s arid residence times of t h e same o r d e r of magnitude as t h a t
r e q u i r e d i n t h e small s c a l e mixer.

Table 6.3. Comparison of D i f f e r e n t Size Mixers

f o r Uranium S t r i p p i n g

Mixer Total Residence Power Stage

Dia, Vol, Flow R a t e , Time, Input, Efficiency,
ft gal !3Pm miri hp/1000 g a l $I

0.5 0,74 0.50 1.5. 5.3 99

3.0 150 76 2.0 30 99
4.0 300 30 LO 5 99

7.0 PHASE SEPARATION

Phase s e p a r a t i o n i s g e n e r a l l y considered a two-step process c o n s i s t -

i n g of a primary break i n which t h e bulk of t h e dispersi-on s e p a r a t e s by
sedimentation and coalescence i n t o i t s component phases, followed by a
secondary break i n which drops of one phase e n t r a i n e d i n t h e o t h e r s e t t l e
out, leaving t h e phases clear. The r a t e of primary break i s t h e c o n t r o i -
l i n g f a c t o r f o r design and o p e r a t i o n of s e t t l e r s . I n b o t h batch and con-
tinuous-flow t e s t s , t h e flow c a p a c i t y of s e t t l e r s w a s determined as a f u n c -
t i o n of t h e mom important variables-type of d i s p e r s i o n , phase r a t i o ,
mixing power,and temperature. The use of a secondary s e t t l e r f o r recover-
i n g s o l v e n t e n t r a i n e d i n t h e r a f f i n a t e was evaluated, and scaleup data were
determined from t h r e e s i z e s of s e t t l e r s . Tlne amount of entrainment of
aqueous i n t h e e x t r a c t and s t r i p p e d solvent and of s o l v e n t i n t h e loaded
cerboriate was measured, but no s p e c i a l e f f o r t w a s made t o decrease it.
Moot of t h e phase s e p a r a t i o n s t u d i e s were d i r e c t e d toward e x t r a c t i o n r a t h e r
than s t r i p p i n g problems because higher f l o w rates and larger equipment a r e
Involved. The b a s i c p r i n c i p l e s of scaleup developed f o r s e t t l e r s i n t h e
e x t r a c t i o n s e c t i o n are assumed t o Spply i n s t r i p p i n g .
 -30-

The amount of entrainment a f t e r 'the primary break i s u s u a l l y not suf-

f i c i e n t t o cause l o s s of s t a g e e f f i c i e n c y due t o back mixing. A s much as
107;backflow of e i t h e r phase CZII be t o l e r a t e d i n e i t h e r t h e e x t r a c t i o i i or
s t r i p p i n g c i r c u i t .22,23 However, entrainment i n t h e streams l e a v i n g t h e
end s t a g e s of t h e e x t r a c t i o n and s t r i p p i n g c i r c u i t s i s important. Loss
of solvent i n t h e aqueous r a f f i n a t e i s economically s i g n i f i c a n t because
t h e uraniu.m concentration i n most f e e d l i q u o r s i s r e l a t i v e l y low. For
example, f o r average uraaium mill l e a c h l i q u o r s , a l o s s of 1 g a l of s o l -
vent p e r 3.000 g a l of r a f f i n a t e i s equivalent t o $/lb of U308 product.

For both batch ani?. continuous-flow t e s t s the solvent w a s 0.1 M

d i ( 2-ethylhexy1)phosphoric a c i d i n kerosene containing 30 g of TBP-per
l i t e r . It w a s scrubbed w i t h 10 v o l of 1 M sodium carbonate s o l u t i o n and
50 v o l of 0.5 M s u l f u r i c a c i d t o remove recadily s o l u b l e components,
thereby making-it s i m i l a r t o p l a n t solvent. The aqueous phase f o r most
t e s t s was a uranium-barren s u l f a t e s o l u t i o n c o n t a i n i a g sodium s u l f a t e and
s u l f u r i c a c i d , although a c t u a l p l a n t l i q u o r s were used i n some Lests
(Table 7.1).

7;1. Batch Primarv Rreak Tests

For t h e bRtch phase s e p a r a t i o n s t u d i e s b a f f l e d tank mixers (Fig. 4.2)

of 3, 6 , and 1 2 i n . d i a were used. A d i s p e r s i o n w a s formed by a g i t a t i o n
a t a power i n p u t s u f f i c i e n t t o y i e l d a uniform di-spcrsion, and t h e break
t i m e w a s t h e time r e q u i r e d a f t e r t h e a g i t a t o r w a s stopped u n t i l a sharp
i n t e r f a c e w a s formed between t h e bu1.k phases.

The g e n e r a l appearance of a d i s p e r s i o n duriilg t h e primary break r e -

sembles a three-phase system i n which a r a t h e r s h a r p l y defined d i s p e r s i o n

.
band is,.sandwiched. between r e l a t i v e l y c l e a r l a y e r s of organic and aque-
ous 6,11 A t one bound.ary t h e r a t e of t r a v e l toward t h e f i n a l i n t e r f a c e
i s dependent on sedimentation of t h e d i s p e r s e d drops and shows l i t t l e
a c t i v i t y . The o t h e r boundary i s c h a r a c t e r i z e d by a c t i v e coalescence of
drops with neighboring drops and w i t h t h e bulk phase which t'ney c o n t a c t .
The coal.escing i n t e r f a c e f o r an aqueous-continuous d i s p e r s i o n i s a t t h e
organic d i s p e r s i o n boimdary, while f o r an organic-continuous dispersioii
t h e coal.escing i n t e r f a c e i s a t t h e aqueous d i s p e r s i o n boundary (Fige 7.1).

A s shown by s e t t l i n g p r o f i l e s (Fig. 7 . 2 ) , t h e r a t e of movement of

b a t h boundaries of s e v e r a l d i f f e r e n t d i s p e r s i o n s in 12-in.-dia b a t c h s e t -
t l e r s i s l i n e a r over most of t h e t o t a l break t i m e . Thfs shows t h a t t h e
r a t e of coalescence i s v i r t u a l l y independent of d5speruioii volwrae and
i n d i c a t e s t h a t most of t h e coalescence occurs a t t h e a c t i v e in'berface
r a t h e r than w i t h i n t h e d i s p e r s i o n . Comparison of s e t t l i n g p r o f i - l e s f o r
aqueous-continuous d i s p e r s i o n s a t A/O phase r a t i o s of 4/1 and 1/1 shows
a f a s t e r sedimentation r a t e f o r t h e d i l u t e , 4/1, d i s p e r s i o n . This causes
packing o f t h e drops toward t h e coalescing i n t e r f a c e u n t i l a close-packed
d i s p e r s i o n i s formed, a f t e r which t h e sedimentation r a t e f a l l s o f f t o
about t h e same rate as t h a t over ,the e n t i r e bres,k t i m e f o r the 1/1
dispersi.on.
 Table 7.1. Physical P r o p e r t i e s of Liquids Use&

~ ~ - ____ - __
I n t e r f a c i a l Tension
Density, Viscosity, with Solvent,

Liquid

Solvent" 0.82 0.80 2.3 1*6

S u l f a t e feed 70 1.0 1.07 1.0 0.70 20 22

Sodium Carbonate 100 1.09 1.08 1.3 0.83 1.5 1.7

Kerr-McGee
Section 10 0.9 0.1 20 0.70 1.4 1.02 0.gl: 18
Holly 1.3 0.1 31 2.0 1.6 1.05 1.07 19
S t . Anthony 1.1 0.1 30 2.2 0.8 1.03 0* 9'7 17
Recycle 0.8 0.1 48 0.94 0.6 1.04 1.03 19
1-9
Shiprock
Kf/l 11
0.7
1.1
0.8
4.1
23 0.34
110 <0,10
1.4 1.02
0.5 - -1.02
Clirmx Uranium
Sand l i q y o r Uo. 19 1.8 2.3 109 1.0 0.7 1.1 1.25 20
Slime l i q u o r , 5/8/58 5.1 3.8 78 ~0.10 0.5 1.08 1.14 18
U, C . Nuclear
Old R i f l e 2.1 2.9 31 1.6 1.4 1.05 1.08 1-9
New R i f l e 4.0 3.1 55 2.5 0.9 1.06 1.10 20

a
-
0.1 M d i ( 2-ethylhexyl)phosphoric a c i d i n kerosene contaiaLrig t r i b u t y l phosphate, 30 g per liter.
 -3 2-3

UNCLASSIFIED
ORNL-LR-DWG 47802

I Active I I

Eventual I n t e r f a c e

Active
Interface ~ +

I Aqueous
_...______ J I ..........

Aqueous-continuous Dispersion Ol-ganic-continuous Dispersion

Fig. 7.1. Illustrations of types of coalescence.

12

E
0
c
0
4
e,
0
$ 8
.-C
2
Q
-
5
0
--I

a
z
2
z 4
0
-.
v,
rr:
w
Q.
-
v,
Q

0
0 40 80 120
TIME, sec

Fig. 7.2. Typical batch settling profiles i n 12-in.-dia seitler.

 -33-
Effect of Mixing Power and Time on Primary Break. Neither mixing
power from 4 to 160 lip/1000 gal nor mixing time from 1 to 30 min had any
effect on primary break time for either aqueous- or organic-continuous
dispersions (Table 7.2). This simplifies the design of mixer-settler
units because the mixing can be selected to optimize stage efficiency
without changing settler capacity.

Table 7.2. Effect of Mixing Power and Time

on Primary Break

Settler: 6 in. aia

Phase ratio, A/O: 1/1
Temperature: 25OC

Mixing Primary Break Time, sec

Mixer Power, Time, Aqueous Organic
hp/1000 g a l min Continuous Continuous

4 10 65
20 64
50 65
160 61.
20 1 46
5 45
10 50
30 49

Effect of Temperature on Primary Break. For both types of disper-

sion, the break time decreased with increasing temperature, from 150 sec
at l5OC to 70 sec at 55OC in a l2-in.-dia settler (Fig. 7.3). Probably
most of the temperature effect is due to a change in the viscosity of
both phases, which decreased in about the same proportion as the break
time with increasing temperature, while density and interfacial tension
were relatively independent of temperature.

Effects of pH and Density of Aqueous Phase on Primary Break. Varia-

tions in the aqueous phase of pH from 0.5 to 1.5 and of density from 1.02
to 1.08 g/ml had no significant effect on primary break time (Table 7.3).
T'nese pII: and. density limits include the variations of most plant leach
liquors .
Plant Leach Liquors. Primary break times for 10 different leach
liquors received from uranium mills on the Colorado plateau were markedly
affected by the type of dispersion (Table 7.4). With most of the liquors
the break time was grea,ter than 300 sec for aqueous-continuous disper-
sions at A/O phase ratios of 4/l and 1/1. However, for solvent-continuous
 -34-

UNCLASSIFIED
OR NL-LR- DWG 47796
181

0 0 Solvent Continuous

e Aqueous Continuous

14r

U
2

r
Wi

k-

e
Y

0.I
M

1O(

6(
10 30 50
TEMPERATURE, O C

Fig. 7.3. Effect of temperature on batch break time i n 12-in.-dia

settler a t 1/1 phase ratio.

F ---
AQUEOUS

--
...___.._J
I I

Fig. 7.4. Single mixer-settler unit for phase separation tests.

 -35-
Table 7.3. Effects of pH and Density on Primary Break Time

Settler: 6 in. dia

Phase ratio, R/O: 1/1
Temperature: 25OC
~-

Primary Break Time, sec

Density, Aqueous Solvent
PI1 g/ml Continuous Continuous

0.5 1.07 50 63
1.0 1.07 50 63
1.5 1.07 57 61.
1.0 1.02 47 65
1.0 1.05 47 65
1.0 1,06 45 63
1.0 1.07 63
1.0 1.08 68

dispersions at phase ratios of 1/1 and 1/2, the break times ranged from
50 to 100 see. In many of the aqueous-continuous tests an emulsion
formed which was stable overnight. A l l the liquors contained silica,
from <O,l to 2.5 g/liter, which could not be removed by centrifugation o r
filtration. The break time with liquors containing less than 0.1 g of
Si02 per liter was about the same as that for sjmthetic sul€ate solu-
tions. At silica concentrations greater than 0.7 g/liter the break time
was greater than 300 sec and a varying araount of stable emulsion was
formed, indicating that silica is the most likely cause of slow phase
separation although it may not be the only emulsifier in the plant
liquors. That silica alone c a n cause emulsion was confirmed by adding
silicic acid to sodium sulfate solutions, which formed an emulsion wiYn
solvent when t h e aqueous phase was continuous and none when the organic
was continuous.

Emulsion Prevention. The majority of the liquors tested contain

emulsifying agents which tend to stabilize an aqueous-continuous disper-
sion. Control of mixing to produce an organic-continuous dispersion is a
simple method of preventing emulsions, Usually organic-continuous mixing
can be maintained by starting the mixer wiYn only solvent present and
then adding the aqueous phase and keeping at least SO$ solvent in the
mixer. If the concentration of emulsifier is very high it may be neces-
sary to maintain greater than 50% solvent to prevent localized formation
of aqueous-continuous dispersion. All except one of t h e solvent extraction
circuits operate with organic-continuous mixing in commercial uranium
mills to prevent emulsions.
 'Table 7.4. Batch Phase Separation T e s t s w i t h
Actual P l a n t Liauors

S e t t l e r : 3 i n . d i a x 3 -5/8 i n . depth
Tempera-Lure: 25OC

Primary Break Time, see

Kerr -McGee

Section 10 0.7 >300 120 80 54

Holly 1.0 >300 >300 62 53
S t . Anthony 2 -2 >300 3300 62 60
13e c yc l e 0.9 >300 >300 82 '93
Shiprock 0.3 E20 110 68 52
KM- I1 <0.1 49 6s 79 p
Climax Uranium
Sand l i q u o r No. 19 1.0 >3QO >300 87 106
Slime l i q u o r <0.1 72 81 53 48
5/8/58
Union Carbide Nuclear Co.
Old R i f l e P l a n t , 1.6 >300 >300 54 51
t r e a t e d wi l;h 1.6 46 61 54 51
Lomar
>300 75 85
New R i f l e P l a n t ,
t r e a t e d with
205
-
3 300
60 75 -
gelatinb
Sodium s u l f a t e
s o l u t i o n , pt1 1.0 <0.1 37 51 53 118
s i l i c T c a c i d added 4.0 - ;300 65 I

a
40 ppm of Lomar PW added t o aqueous phase.
b S i l i c a coagulated by a d d i t i o n of 300 ppm of g e l a t i n t o aqueous and
removed by c e n t r i f u g a t i o n .

Another method of preventing emulsions that has been s u c c e s s f u l i n

l a b o r a t o r y t e s t s i.s t h e a d d i t i o a of c e r t a i n s u r f a c t a n t s to t h e aqueous
f e e d b e f o r e c o n t a c t with t h e s o l v e n t . CatioLiiC types, e.g. Lomar PI/,*

%omr iT i s t h e sodium salt of condensed mononaphthalene s u l f o n i c a c i d ,

PL
a v a i l a b l e from Jacques Wolf and- Co.
 -37-
have been most e€fecl;ivc. Addition of %bout 40 ppm to the ~iqu.eousliquor
will permit mixing with either phase contifiuoim without emulsion f o r m -
tion8 ('i'tzble 7.4).

In cases where silica 21 ne is the cause of enulsion the silica can

be flocculated with After filtration or settling out of the
sil.ica, the queous phxe e m be contacted w i t h solvent without diffi-
culty (Table 7 . b ) . Flocculating agents thzt are normally uscd Lo aid in
settling ore slimes are noT; very effective for flocculation of silica,

7.2 Continuous-flow Settler Tests

For the continuous-flow settler tests a single mixer-settler unit

(Fig. 7.4) was usea in which both the solvent and aqueous phases of con-
stant composition were recycled. The mixer was a bzflt'led tank agitated
with a flat bladed turbine and the settler w a s :I. cylindrical t a r & in
which the total liquid depth w a s approximately 30 in. The interface was
controlled near the midpoint of the settler by a gra.vity leg on the
aqueous discharge. Three sizes, 0.5, 1.8, and 4 ft dia, were used to
obtain scaleup data. The temperature was azintzined at 2 5 O C except where
noted otherwise.

Correletion of S e t t l e r Capacity with Dispersion Band Thickness. A t

steady state there was at the interface a distinct dispersion b<md which
was of uniform thickness across the entire area of the settler, very
I

similar to previously reported observations with other systems5'. Steady

state was usually attained within 20 min of operation and the dispersion
thickness was measured over a period of 1 hr, The band was stable with
respect to operation time, 7 hr being the longest time tested. The dis-
persion thickness increased exponentially with increased f l o w rate with-
out showing a sharp flooding point, The best correlation was obtained by
plotting dispersion thickness against flow rate of dispersed phase per
unit settler'area (Figs. 7.5 and 7.6). 'The result is a family of nearly
parallel lines showing relatively small effects of phase ratio and settles
diameter for both aqueous- and solvent-continuous dispersions.

The data were summarized by arbitrarily selecting a flooding point

at a dispersion thickness of 2 ft, This is somewhat justified because
usually a total liquid depth of 2 ft is sufficient for simple gravity leg
control of the interface position with most systems. The nominal flow
capacity was chosen to be the flow at 5 in. dispersion band,which was
about half the flow rate that produced flooding (2-ft band), thereby
allowing a safety factor of 2 for design purposes.

Effect of Phase Ratio and. Type of Dispersion, The nominal flow

capacity for organic dispersed fn aqueous increased from 0.9 to 1.4 gpm/
ft* as the O/A ratio was increased from 1/4 to 1/1 (Table '7.5). Simi-
larly, the nominal f l o w of aqueous dispersed in organic increased from
1.0 to 1.4 g p m / f t 2 as. the A/O ratio was increased from 11%
t o 3/l.
 UNCLASS I FlED
ORNL-LW-DWG 55789 I
_ -

.-C 10

0.4

0
1 .o

A/O =
2/1
3.c
ORGANIC FLOW RATE,
gpdft2
1/1
/,
1.4
1 ‘
1.0
(b)
I
........
4.

A 3/1
n 4/ 1

Fig. 7.5. Effect of phuse ratio on phuse se ration i n 4-ft-dia

settler, (a) Aqueous continuous. (b) Organic continuous.
 -39-

40r-----
U NCLASSI FI ED
ORNL-LR-DWG 47795

ORGANIC FLOW RATE, AQUEOUS FLOW RATE,

gpm/ft* 9Pdft2
A/O Phase Ratio Settler Dia, ft A/O Phase Ratio Settler Dia, ft
1/1 4/1 1/1 1/2
0 e 0.5 0 0 0.5
SI 8 1.8 0 8 1.8
A A 4.0 A A 4.0
L 7.0
a - 16.0
Fig. 7.6. Comparison of settler size. (a) Aqueous continuous.
6) Organic continuous,
 Table 7.5. E f f e c t of Phase R a t i o on Nomi.nal FI-ow C a p a c i t p

R a t i o of
Dispersed t o Flow Rate of Dispers3d Phase, gpm/ft2
C ont iiiuous Aqueous Organic
Phase c o i t inuous Coniinuous

1/4 O.? z. .

i/3 0 .? rn

J-/2 1.2 1.0

1/1 1.4 1.2
2/1 1.4
3/1 I 1.11.

%able derived from Fig, 7.5.

Organic-continuous mixing -das maintained. a t A/O r a t i o s as high as

3b-, i.e. t h e major phase W'LS d-ispersed. This was accomplished by s t a r t -
i n g t h e mixer with only s o l v e n t p r e s e n t and t h e n s t a r t i n g t h e aqueous
flow. The d i s p e r s i o n w a s much more viscous t h a n when t h e minor phase was
dispersed, b u t t h e r e w a s no marlied e f f e c t on t h e rate of phase separatLon.
When t h e r a t i o of d i s p e r s e d phase t o continuous was increzsed t o h/1. o r
g r e a t e r , i n v e r s i o n occurred t o form a d i s p e r s i o n with t h e major phase
continuous, and i n t h e presence of s i l i c r , i n v e r s i o n occurred a t lower
r a t i o s . Therefore f o r pl-ant p r a c t i c e it i.s d e s i r a b l e t o maintain t h e
r a t i o of d i s p e r s e d t o conbinuous phase l e s s than 1/1.

The nominal flow c a p a c i t y of d i s p e r s e d phase was s l i g h t l y g r e a t e r

for aqueous continuous t ~ m nfor organic continuous, le2 vs 1.0 gpm/ftp a t
a phase r a t i o of 1/1. The effect of type of d i s p e r s i o n i s g r e a t e r w i t h
s e v e r a l amines used i n t h e Amex process,26 and i n d i c a t e s t h a t nominal
flow c a p a c i t y decreases with increased vn'.scosity of t h e continuous phase
and decreased- i n t e r f a c i a l t e n s i o n .

E f f e c t of Temperature. Nominal flow c a p a c i t y i n c r e a s e d n e a r l y

l i n e a r l y with increased temperature over t h e range 1-5 t o 45oC, being
n e a r l y doubled f o r 30°C teniperature r i s e (Table 7.6, Fig. 7.7). This
agrees with t h e temperature e f f e c t observed i n b a t c h t e s t s , where it was
shown t h a t the decrease o f primary break ti.me with increased temperature
corresponds roughly with Yne change of v-iscosity with temperature.

The temperature i n most uran2um m i l l . s o l v e n t e x t r a c t 3 on c i r c u i t s

depends on ambient conditions ,md i s u s u a l l y w i t h i n t h e range 15 t o 45OC.
Because of t h e r e l a t i v e l y 1-artge temperature e f f e c t on s e t t l e r flow
capacity, s e t t l e r s i z e should be designed for t h e minimum temperature
expected o r f a c i l i t i e s t o r h e a t i n g t o design temperatarc should be
provided .
I
 UNCLASSIFIED
OR NL -LR-DWG 47800
2.0

8m

W'

2
E
a 1.6
LU
v)
PL
Q
u1
vr
5
5
53
W

1.2
9u.
d
f
E
0
z
0.8
IO 30 50
TEMPERATURE, "C

Fig. 7.7. Effect of temperature on nominal flow capocity of

6-in.-dio settler for A/O phase ratio of 1/1.

Distributor Box

Distributor

Circular Flow Transverse Flow

Fig. 7.8. Flow patterns (plan view) i n 4-ft-dia settler.

Perforated Plate Slotted Plate

Fig. 7.9. Distributor outlets i n 4-ft-dia settler.

 -42-

Aqueous continuous 1.5 0.95 4.7

1,49 1-9 3
0

25 0.68 0.8
1.35 4.4
2.03 17.0

35 1.89 6.11.
2*57 20~8
45 1.89 4..3
2. '70 18.4
Organic continuous 15 0.6% l,8
35 19.0

2j 0.68 1.5
1..35 6.3
1.84 23,O

35 0.68 0.4
1-35 3.3
2.03 13.8
45 2.03 5.5
2.70 1'7 * 8

E f f e c t of Mixing Power. Power input; t o t h e mixer w a s v a r i e d from

zero t o 90 h p / l O O O g a l without e f f e c t 011 d i s p e r s i o n t h i c k n e s s i n t h e s e t -
t l e r (Table 7.7), confirmi-ag t h e observed back of dependence o f batch
break t i m e on power i n p u t . 'The t e s t s were m d e w i t h a 1 2 - i n e - d i a mixer
and a 4-ft-din. s e t t l e r , using a n aqueous-continuous d l s p e r s i o n writh equal
flow of each phase ( 2 " 5 gprn/ft2). The turbulence i n the mixer a t t h i s
flow r a t e was s u f f i c i e n t t o cause mixins with t h e agl.tator s h u t o f f .
Independenc? of phase s e p a r a t i o n from nixing power s i m p l i f i e s t h e design
of m i x e r - s e t t l e r s because t h e power i n p u t can be chosen t o optimize
e x t r a c t i o n e f f i c i e n c y without a f f e c t i n g s e t t l e r capacjty.

Flow P a t t e r n s in t h e S e t t l e r . Tvo flow p a t t e r n s i n t h e Lc-ft s e t t l e r

were i n v e s t i g a t e d ( F i g . 7.8). One p a t t e r n was c i r c u l a r , formed when the
mixed phases were i n t r o d u c t c d through a d . i s t r i b u t o r box vhich was a 45O
 -43-

Table 7.7, Effect of Mixing Power on Dispersion B a d

Mixer: 12 in. dia
Settler: 4 ft dia
Flow rate, each phase: 2.5 gpm/Pt2
Phase ratio: 1/1
Continuous phase: aqueous

Turbine Power Input, Dispersion Sand

h 1000 a1 Thickness in.

6 0 0 18
200 4 22
300 15 21
400 40 23
550 90 22

3 1340 40 22

sector of the settler with a distributor outlet located 315' from the
settler outlets. An unbarfled distributor box was compared with boxes
having either a perforeted plate or a slot as the distributor outlet
(Fig. 7 . 9 ) . The other flow pattern was transverse, the result of feed-
ing the mixed phases at the side opposite the outlets. Them was no
marked difference in dispersion thickness with any of the flow patterns
tested (Table 7.8).Because there was a distinct dispersion b m d in the
distributor box which was only slightly thicker than that in the rest of
the settler, the transverse flow pattern w a s used in subsequent tests.

Ve-rtica.1 location of the point of entry of the mixed phases in rela-

tion to the dispersion band was important in the O.5-rft-dia. settler.
Introduction of the feed either above or below the dispersion band re-
sulted in a thicker band than that obtained when Yhe feed entered near
the midpoint. Although this was not observed in the larger settlers, the
feed point was standardized at the rnidpoint of the dispersion band.

bTa11 Effects. When the settler wall was preferentially wetted by

the dispersed phase, water drops on glass or solvent on plastic, coales-
cence was observed on the wall and the dispersion brznd was thinner than
when the dispersed phase did not wet the wall (Table ' 7 . 9 ) . The wall
effect is greatest in small-diameter settlers where the ratio of wall
area to cross sectional area is large. Consequently the wall effect
should be minimized for valid comparisons of s m l l and l a r g e settlers.
For the 0.5-ft-dia settler, glass w a l l s were used for acpeous-con"cnuous
dispersions and a plastic liner, nonaqueous wetted, was inserted for
solvent-continuous dispersions. For the larger settlers (1.8 and 4 ft),
which were constructed of stainless steel, no attempt was made to mini-
mize t h e wall effect.
 -44-

Table 7.8 Comparison of Flow P a t t e r n s i n I+-ft-dia S e t t l e r

Organic-continuous dispersion, phase r a t i o 1/1

Dispersion Thickness, i n .
Aqueous Flow Aqueous Flaw
Flow P a t t e r n 0.83 g p / f t 2 2.0 g-pm/ftc'

Circular
D i s t r i b u t o r box w i t h p e r f o r a t e d pl-ate L.3 10
D i s t r i b u t o r box with 3 x 18in. slot 3.0 18
D i s t r i b u t o r box with 24 x 32 in.
opening 2,4 14
Transverse flow 2-3 16

Table 7.3. Nall E f f e c t on Dispersion Thickness

i n 0.5-f't-dia S e t t l e r

A/O Aqueous
Continuous Phase Flow Rate, Dispersion Tinickness, i n .
Phase Ratio gpm/f t 2 Glass Wall P l a s t i c Wall

Aqueous 1/1 1.35 4.4 2.4

Organic l/J- 1.35 2.8 "I. 0
1-84 9.3 23
2.8 11
9.9 >27

'7.3 Scaleup of S e t t l e r s
Dispersion thickness as a f u n c t i o n of flaw r a t e p e r u n i t cross-
s e c t i o n a l a r e a i s v i r t u a l l y independent of s e t t l e r diameter for aqueous-
continuous d i s p e r s i o n a t A/O r a t i o s o f 4/1 and l/1 and f o r solvent con-
tinuous a t 1/1 and 1/2 (Fig. 7.6). Therefore scaleup can be based. on
c o n s t m t flow r a t e per square f e e t ana constant d i s p e r s i o n thickness.

Summarizing t'ne d a t a &s nomirial f l o w c a p a c i t y of t h e dispersed phase

demonstrates t h i s more cJ-early (Table '(.lo). The nominal flow c a p a c i t y
was read from Fig. 7.6 a t 5 i n . d i s p e r a i o n t h i c k n e s s a n d i s about h a l f
t h e f l o w rate causing flooding f o r a t o t a l l i q u i d depth of 2 ft, The
nominal flow c a p a c i t y of dispersed phase ranges from 1,O t o 1.5 e;pm/ft3
 -45-

Table 7.10. Nomlnal Flow C<ipa.eityof Dispersed Phase

Settler Flow Rate of Dispersed Phase, gpm/St2

Dia, Area, Aq Continuous Org Continuous
ft ft2 A/O = 4/1 n/o = 1/1 n/o = 1/1 A I 0 = 1/2

0.5 0.2 1.1 1.4 1.1 1-0

1.8 2.6 1.2 1.4 1.5 1.2
4.0 1.4
7 .O
12
38 -
1.0

-
-
-
1.1
I
1.0
1.0
16.0 190 1.0

for all v a r i a t i o n s of phase r a t i o and f o r both types of d i s p e r s i o n i n

s e t t l e r s 0.5, 1.8, 4.0, 7, and 16 f t dia. Over-all, t h i s represents an
area scaleup of n e w l y 1000-fcld.

The d a t a f o r 7- and 16-ft s e t t l e r s were obtained from commercial

Dapex process c i r c u i t s i n uranium mills ( d e t a i l s i n Sec. 8.0), which con-
f i r m t h e p r a c t i c a l use and v a l i d i t y of t h e scaleup r e L i t i o n s . Because of
unlinown f a c t o r s t h a t could a f f e c t phase s e p a r a t i o n , Plow c a p a c i t y t e s t s
should be made w i t h r e p r e s e n t a t i v e samples of a c t u a l p l a n t s o l u t i o n s .
The scaleup d a t a i n d i c a t e t h a t t h i s can be done i n s e t t l e r s as small as
0.5 f t dia t o provide a r e l i a b l e b a s i s for design of l a r g e - s c a l e equipment.

7.4 C o r r e l a t i o n of Ratch and Continuous S e t L l i n ~

An a c c u r a t e c o r r e l a t i o n of b a t c h primary phase s e p a r a t i o n w i t h
continuous-flov c a p a c i t y has fiot been p o s s i b l e with t h e p r e s e n t data.
However, i n both cases t h e r a t e of coalescence appears t o be dependent on
t h e area of t h e coalescing i n t e r f a c e and n o t on t h e d i s p e r s i o n volume.
The l i n e a r r a t e of movement of t h e a c t i v e i n t e r f a c e i n batch t e s t s should
r e p r e s e n t t h e l i m i t i n g v e l o c i t y t h a t could be a t t a i n e d in a continuous-
flow s e t t l e r . This w a s tested by using t h e l i n e a r rate f o r t h e coalesc-
i n g i n t e r f a c e from t h e b a t c h p r o f i l e (Fig. 7.2) t o c a l c u l a t e t h e maximum
flow c a p a c i t y of t h e d i s p e r s e d phase. The r e s u l t s i n d i c a t e flow rates of
3.2 gpm/ft* a t A/O of 1/1for aqueous-continuous d i s p e r s i o n s and 2.6 gpm/
f t * f o r organic continuous. These a r e both s l i g h t l y g r e a t e r t h a n a c t u a l
f l o o d i n g c a p a c i t y measured i n continuous-flow t e s t s , being equivalent t o
n 40-in. d i s p e r s i o n t h i c k n e s s (Fig. 7.6). So it may be concluded t h a t
batch t e s t s are u s e f u l as a rough method of p r e d i c t i n g continuous-flow
c a p a c i t y i n a d d i t i o n t o demonstrating t h e r e l a t i v e e f f e c t s of mixing
power, tp,mperaturc, and type of d i s p e r s i o n .

7.5 Entrainment i n E x t r a c t i o n S e c t i o n

Entrainment i n b o t h s o l v e n t and aqueous streams w a s measured 8 s a

p a r t of t h e continuous-flow t e s t s of s i n g l e - s t a g e m i x e r - s e t t l e r u n i t s t o
determine tlne effects of phase ratio, temperature, and flow rate. A
secondary settler was tested for recovery of solvent entrained 3.n the
aqueous phase e

A centrifugation me-t'nod was developed measuring the amount of sol-

vent entrained in the aqueous. It consi sts in centrifuging 25O-ml samples
in a bottle with a neck calibrated in 0.0l-nil. divisions. Tests with
-
spiked samples shoved. an accuracy of -t- 20% for samples containing as
little as 0.04 gal of solvent/1000 gal aqueous. Aqueous entrainulent in
solvent was determined by centrifugation of 140-ml samples in calibrated
(0.01-ml. divisions) cone-bottom tubes,

Solvent En-traiment in Aqueous. The type of dispersion formed during

mixing ha,d a significant effect on solvent entrainment in the aqueous

.
phase after primary phase separation. The entrainment was consistently
lover f o r organic-continuous dispersions than for aqueous-continuous
Solvent entrainment was less than 0.2 gal/l000 gal i n 0.5-ft (Table 7.l6),
l+---ft(Table 7.12), and plant settlers (Sec. 8.0) for solvent-continuous
mixing at flow rates up to flooding and at h / O phase ratios ranging from
&I to 3/1. F O ~typical application of the Dapex process in uranium
milling plants, the cost of solvent lost by entrainment at this level is
about I-# per pound of U308 recovered, which is leas than the estimated
c o s t of reagent lost by-solubility.9

Solvent entrainment for aqueous-continuous mixing increased both

with increased A/O phase ratio and flow rate, w i t h some inconsistencies
between il.aLa for 0.5- and ll--ft-diasettlers, The effect of phase ratio
at constant aqueous flow rate (1.35 gpna/tt2) in Table 7.11 shows ?Anat
solvent entrainment is about an order of magnitude higher at h / l than at
l/1*
The effect of f l o w rate at an A/O phase ratio of I C / l is more marked
in the 0.5- than in the 4-ft-dia settler; solvent en-trainment increased
from 1.0 to 6.2 ga1/1000 gal. as tlie aqueous flow rate was increased from
1.35 to 5.4 g p m / f t 2 (Table 7.13).
Table 7.11. Effect of Phase Ratio on Solvent Entrainment

Aqueous flaw x-ate: 1.35 g p m / f L 2

Temperature: 25%
- ~- - .. - __
Solvent i.n Aqueous,
-
C ontiiiuous

Aqueous 1.0 2.0

<O .Ob 0.3
Organic <O .04 <0.2
<o .04 <0.2
 -47-

Table 7.12. Solvent Entrainment Data for 4-ft-dia Settler

Temperature: 25OC

Aqueous
A/O F l o w Rate, Solvent in Aqueous, ga1/1000 g a l
Phase Ratio gpm/ft2 Aqueous-continuous Solvent-continuous

4/1 1.67 2.1

3.33 2.o
5.00 2.4

3/1 1.25 2.3 <0.2

3.75 2.2 <0.2
5.00 2.2 <O .2

1.67 1.1 a.2

2.50 1.0 <0.2
3*30 1.7 c0.2
5.00 1.6 c0.2

0.83 0.4 c0.2

1.25 0.3 a. 2
1.67 0.2 c0.2
2.08 0.5 x0.2
2.50 0.2 <0.2

1/2 0.42 0.3 c0.2

Table 7.13. Effect of Aqueous Flow Rate on Solvent Entrainment

A/0 phase ratio: 4/1

Temperature: 25OC
Dispersion: aqueous-continuous

Solvent in Aqueous,
Aqueous Flow Rate, ga1/1000 gal
gpm/f t2 0.5-ft-dia Settler 4-ft-dia Settler

1.35 1.0 ..
1.67 2.1
..
I

2.70
3.33 -
2.2
2 .o
.
4.35
-
3*8
5.00
5.40 6.2 -
2.4
 -48-
I n c r e a s i n g thr temperature from 25 t o 50°C reduced s o l v e n t e n t r a i n -
ment 4- t o 5-fold a t an A/O r a t i o of 4/l (Table 7.14-),b u t it w a s sti.ll.
higher t h a n t h a t obtained f o r organic-continuous mixing.

Table 7.14. E f f e c t of Temperature on Solvent Zntrainment

S e t t l e r : 0.5 f t d i a
A/O phase r a t i o : 4/1
I)is p e r s i o a : aqueous -continuous

15 2 .o 5.6
25 1,O 3 90
35 0.6 2.6
50 0.4 1.6

Aqueous Entrainiiient i n Solvent. Entrainnient of aqiieous f e e d i n t h e

ex.tract i s not an important econoroic f a c t o r but 1s of i n t e r e s - t because
carryover can contarninate t h e s t r i p p i n g c i r c u i t and t h e uranlum product.
I n all %ests t h e aqurous entrainment was l e s s t h a n 1 v o l $ o f t h e s o l -
vent. For a t-yptcal Dapex uranium i n s t a l l a t i o n where t h e r a t i o of f e e d
l i q u o r .to e x t r a c t i s 4/L, an entrainment value of 1 v o l $ would r e s u l t i n
a r a t i o of each con'taminant t o uranium i n t h e e x t r a c t of 1/400 of t h a t i.n
the f e e d l i q u o r . For average mill l i q u o r and p r e s e n t product s p e c i f i c a -
t i o n , t h i s amount of contamination woiild be unimportant.

Secondary S e t t l e r f o r Recovery of Hntrained Solvent. Although i t

has been demonstrated tha,t organic-continuous mixing i s d e s i r a b l e t o
avoid emulsions %id t o mi.nimize s o l v e n t entrainment, t h e r e are s i t u a t i o n s
due t o e x i s t i n g equipment l i i n i t a t i o n s where .the system i s operated
aqueous-continuous and it i s d e s i r a b l e t o rec3.uce t h e amount of s o l v e n t
l o s t 'oy entrainment. A secondary s e t t l e r of t h e type irsed by t h e p e t r o -
leum i n d u s t r y t o remove o i l from waste water27 decreased s o l v e n t e n t r a i n -
ment from ax average of 3 t o l e s s than 0.2 ga1/1000 g;.".l a t an aqueous
flow rate of 2 a m (Tahle 7.15). Thi.s i s e q u i v a l e n t t o 25 min residence
t i m e in t h e s e t t l e r . F i l l i n g t h e f i l m r u p t u r e chamber w i t h various pack-
i n g s such as T e l l e r e t t e s , T u f f i e s , OT o i l s h a l e which were s o l v e n t wetted
d i d not decrease entrainment l o s s . R s i n g l e mi.xer-settler u n i t was
operated aqueous-continuous a t an A/O r a t i o of 4/1 t o supply aqueous phase
containing e n t r a i n e d s o l v e n t t o t'ne secondary s e ' i t l e r ( F i g . 'f.lO), which
wes evaluated by measuring t h e entrainment i n t h e aqueous phase l e a v i n g
it. The secondary s e t t l e r was a. r e c t a n g u l a r box 6 by 1 by 1.5 ft high
with a flow d i s t r i b u t o r t o promote low tul-b.ulence i n t h e s e t t l e r where
e n t r a i n e d s o l v e n t drops would r i s e and. form a layer which could be r e -
claimed, Thz l i q u i d depth w a s 1. St, s e t by a f i x e d g r a v i t y leg on the
aqueous drischargc.
 -49-

Table7.15. Evaluation of Secondary Settler for

Reducing Solvent Entrainment in Aqueous

Solvent in feed: 3 ga1/1000 gal

Packing in P r e s sure Aqueous Solvent

Rupture Coalescer in Drop, Flow Rate, Entrainment,
Chamber Filter Frame in, HpO gpm gal/lOOO gal

None . I 2 0-16
T e1ler et,tesa 2 0.20
Tuff ies 1 0.10
O i l shaleC I .. 1 0,lO
None GLas s wool 2.5 2 0.04
None Glass wool 2.5 4 0.04
None 1 sheet of glass clothd 2 0.13
None 1 sheet of glass clothd - 4 0.14
None 4 sheets of glass clothd 2.3 2 0.04
None 4 sheets of glass clothd 3.3 4 0.04
__
?Polyethylene tower packing, IIasahaw Chemical Co.
b\qoven polyethylene scouring pad, SOS Co.
C
Oil shale, 3/8 in.
$iberglas cloth, Code N41R40, Owens Corning Fiberglas Co.

To test various coalescing media, a filter frame (area 1 )'

t
f was
inserted in the vertical plane at position C (Fig. 7.10). Glass wool mat
and glass cloth reduced entrainment to c0.04 gal/l000 a't flow rates up 'to
4 Lg?m with a pressure drop of 2-3 in. H2O. Dyne1 cloth caused a pressure
drop greater than 6 in. I$O at n flow rate of 1 a m , which caused the
aqueous phase to flow over the top of the filter f s m e making evaluation
impossible.

The practical usefulness OS coalescing media in the secondary settler

probably would depend on the amount of slime in the aqueous phase, which
would blind the coalescer and cause an excessive pressure drop. The
coalescer could be backwashed by reversing the direction of aqueous flow
os by wash nozzles. The slime problem w a s not studied; therefore the
fin81 feasibility of coalescers should be determined with actual plant
raffinates.

7.6. Phase Separation in Stripping Circuit

Phase separation tests of the uranium stripping circuit using sodium
carbonate was not investigated as thoroughly its extraction because the
f l o w rates are relatively smaller and settler sizing is not so important
 -50-

U NCLASS1 F I E D
OR NL-LR-DWG 49128

0
I
I Q
T
1'

I
I
I
_I-
......

Plan

" I
i1 -'1/2'

El eva tis r I
......... 6' ..........

Fig. 7.10. American Petroleum Institute type secondary settler. (A) Film
rupture chamber; (8) distribution box and adjustable weir; (6) f i l t e r frame;
(D) sample point.

Solvent,

\h
Aqw eo us

S'
1 .

--I
f I v e n t
+------- 7' .
-

Fig.. 8.1. Climax mixer-settler.

 -51-
econon7ically. Scouting t e s t s were made i n t h e 0.5-ft-dia s e t t l e r w i t h

2
mixtures of s o l v e n t and LO$ N q C O s o l u t i o n s (Table 7.1). The mixing was
c o n t r o l l e d t o produce organic-con inuous d i s p e r s i o n wit'? a phase r a t i o
(A/O) of l/6 i n most tests, which i s i n t h e range of t y p i c a l s t r i p p i n g
c i r c u i t s . Only a t h i n d i s p e r s i o n band w a s d i s c e r n i b l e a t a phase r a t i o

7.16) .
of 1/6 and t h e t h i c k n e s s i n c r e a s e & very l i k t l e with increased flov (Table
However, t h e entrainment of aqueous i n s o l v e n t i n c r e a s e d sharply,

Tzble '9.16. Phase Separation for S t r i p p i n g C i r c u i t

Settler: 0.5 f t d i a

Entrainment,
ga1/1000 gal
Flow Rate, Dispersion Aqueous Sol.ient
Continuous A/O gpm/ft2 Thickness, in in
Phase Phase R a t i o Aq. Org. in. Solvent Aqueous

0r g a n i c 1/6 0.14
0.27
0.84
1.6
<0.1
0.1
7.0
7.0
.
<O 04
<O .Ob
0.41 2.4 0.3 7.7 <0,04
0.54 3.2 0.4 27.3 <O ,04

1/1 0.34 0.34 0.8 1.3 <O. 04

0.78 0.78 14. 0.7 <o .ob-
Aqueous 1/1 0.54 0.54 1.3 2.1 <0.04

approachlng t h e flooding p o i n t where t h e entrainment was e q u a l t o t h e

phase r a t i o , 1/6, of t h e f e e d t o t h e s e t t l e r . The sharp i n c r e a s e in en-
trainment occurs between a s o l v e n t flow r a t e of 2.4 and 3.2 gpm/ft*, so a
good choice for t h e maximum p r a c t i c a l s o l v e n t flow c a p a c i t y i s 2 gpm/ft2
which could be used as a b a s i s f o r design. A t higher flow r a t e s t h e
amount of entrainment i s l a r g e enough t o be economLcally important be-
cause of l o s s of sodium carbonate, and t o lower s t a g e e f f i c i e n c y as a
r e s u l t of back-mixing of t h e aqueous phase between s t a g e s ,

T e s t s a t a phase r a t i o of 1/1 showed t h a t r e c y c l i n g of aqueous would

lower entrainment, b u t t h e flow c a p a c i t y would be reduced because a
d i s p e r s i o n band formed a t t h e i n t e r f a c e s i m i l a r t o t h a t obtained i n t h e
e x t r a c t i o n c i r c u i t . This l i m i t e d t h e s o l v e n t flow c a p a c i t y t o about
0.6 gpra/ft2 a t a 5-in. band, which i s only about 25% of t h e c a p a c i t y a t a
phase r a t i o of 1/6.

Entrainment of s o l v e n t i n aqueous was very l o w i n a l l t e s t s ( ~ 0 . 0 4

gal/1000 g a l ) . It should be noted, however, t h a t t h i s system contained

.
no i m p u r i t i e s o r s o l i d s which might t e n d t o i n c r e a s e t h e entrainment
lasses
 Tes.ts of t h e s e t t l e r f o r t h e s t r i p p i n g c i r c u i t were not scaled up.
However, the d a t a obtained. i n the uranium mri.1.1. Ilspex c i r c u i t s (Sec, 8.0)
showed s a t i s f a c t o r phase s e p a r a t i o n i n 7 - f t - d i a s e t t l e r s a t a solvent Slo:.~
rate of l , 8 e;pm/ft5, which agrees w i t h t h e flow cap-city determined i n
t h e small-scale equipment. It may t h e r e f o r e be concluded t h e set'ilers
can be scaled. up a t constant flow rate per u n i t c r o s s - s e c t i o n a l a r e a .

The f i r s t commercial q q l i c a t i o n of solvent e x t r a c t i o n i n uranium

m i l l s was by Kerr-McGee O i l I n d u s t r i e s , Shiprock, N . M., and C l i m a x
Uranium Co., Grand Ji.inction, Colo., i n September 1956. Both mills i n -
s t a l l - e d t h e Dapex process without a c t u a l p i l o t p l a n t operation. 'The
design was based 011.d a t a obtained. from bench-scale labora'Lory counter-
c u r r e n t tests and t h e b a s i c p r i n c i p l e s of mixing and phase s e p a r a t i o n ob-
t a i n e d from t h e u n i t o p e r a t i o n s stud-y zt ORNL. Since t h e e x t r a c t i o n
equipment at Climix i s almost exacLly t h e same 8,s t h e models described
above? o p e r a t i o n a l d a t a from t h e s e mills provide a good chzck of t h e
scaleap r e l a t i o n s d.eveloped i n t h e small-scale t e s t s . Throirgh t h e cour-
t e s y of t h e Kerr-McGee and Climax managements, both m i l l s were v i s i t e d . i.n
May 1958 to obtain samples a.nd i n f o r m t i o n r e q u i r e d i n analyzing perform-
ance of t h e p l a n t equipment.

8.1 Cliaax uranium Company

'The m i l l . uses the s a l t - r o a s t process f a r recovering urarriun and vana-
dium from ores. The Dapex s o l v e n t e x t r a c t i o n process i s uswl f o r r e -
covery of uranium from s u l f u r i c a c i d l e a c h of r e s i d u e s a f t e r most of the
vaiindium has been removed. T m solvent i s 0.08 M D2EWA end 3% TBP dis-
solved i n kerosene o r lie. 1 f u e l o i l . The aqueous f e e d i s P i l t e r e d
through drum f i l t e r s ami although not sparkling, u s u a l l y con'tains less
than 0.5% i n s o l u b l e solids, Typical a n d y s i s of t h e feed, i n grams p e r
l i t e r : 1J 5 . 2 , V 4.0, Pe 0 . 3 , Al 3, Mo CO.1, SO4 (0,C 1 2 , anrl PO4 2;
pH 0 . 5 . The l i q u o r i s h i g h l y oxidized so t'nat t h e vsnadium i s p p e s e n t i n
t h e pentavzlent s t a t e .

The uranium i s extracted. i n four s t a g e s ( s i x i - n s t a l l e d ) and strj.pped.

w i t h 1. M N a 2 C 0 3 i n f o u r s t a e c s . 'The flow r a t e s of feed, s o l v e n t , and
s t r i p a r e 40, '70,and 6.6 gpm, producing a .loaded s t r i p s o l u t i o a contain-
i n g aboiit 50 g of uranium per l i t e r . The u r a n i u a i s recovered, a f t e r
d e s t r o y i n g t h e carbonate w i t h s u l ' f i i r i c a c i d a t p11 4, by p r e c i p i t a t i o n
w i t h ammonia a t p H 7. The p r e c i p i t a t e is f i l t e r e d and cal.cined at 900°C.

The process i s con.trol.led by r e g u l a t i n g t h e flow r a t e s of aqueous

feed, solvent, and. sodi-um carbonate. The s o l v e n t and carbonate flow
rates are a d j u s t e d according t o feed concent,rati-on and flow r a t e t o IlkziiT-
Lain h i g h uranium 1oad.i.ng i n t h e solvent without excessive l o s s of uranium
i n t h e r a f f i n a t e . Each stream flows by g r a v i t y from a Constant-level
head tank ana i s metered by a recording rotameter.
 -53-
The mixer-settlers are the same size in the extraction and stripping
circuits (Fig. 8.1). They were designed based on extraction requirements
and are slightly oversized for stripping service. The mixers zre wooden
tanks (3 by 5 ft), which are a direct scaleup of the small model shown in
Fig. 1+.2. The agitator is a flat-bladed turbine, 1 ft dia, driven by a
5-hp motor at 380 rpm, which results in a power input of 30 hp/lOOO gal.
The mixing is controlled to maintain the solvent phase continuous to
avoid emulsions caused by silica or solids. The settlers are wooden
tanks (7 by 5 ft) with a horizontal settling area of 38 ft2. The inter-
face level is controlled by an internal aqueous gravity leg. The mixer-
settlers are installed on a grade so that the solvent flows by gravity
between stages and .the aqueous is advanced by air-lifts.

Uranium Profile. The concentration of uranium in each phase leaving

the settlers was determined; the resulting profile is shown in Fig, 8.2.
In the extraction circuit the uranium concentration of the aqueous phase
was decreased from 5.2 to 0.014 g/liter in four stages, giving 93.7$ re-
covery of uranium. In the stripping circuit the uranium. in the solvent
w a s effectively removed in four stages. The profile shows back-extraction
of uranium in the No. 1 stage, which can occur when the pB of the aqueous
carbonate is too low. The profile also shows that the uranium content of
the aqueous phase from stage No. 4 is considerably greater than that cal-
culated by material bal,ulce from the solvent stream entering and leaving
that stage. The most logical cause is back-mixing of aqueous from No. 3
stage due to entrainment of aqueous in the solvent. Based on material
balance, the entrainment would be 3 vol $, which is reasonable at the
operating A/O phase ratio of 1/10 and temperature of 32OC. The entrain-
ment was not measured, but t'nief samples of the Pio. 1 and No. 4 settlers
showed that the aqueous content of the solvent was about 5% within 4 in.
of the top of the solvent layer.

The loaded aqueous carbonate stream leaving the strip circuit con-
tained am insoluble yellow solid (1 wt $), analysis (dry) of which showed:

u . 45.4 wt $3

v 9.8
The U/V/Na mole ratio was very nearly 1, indicating that the solid is
prob8bly synthetic carnotite. The vanadium in the solid represents about
65% of the total vanadium present in the loaded s t r i p . Separation of this
solid m y offer a simple method of decreasing the v;33ladium content of the
final uranium product.

Stage Efficiency, The stage efficiencies (Table 8.1) of the mixer-

settlers were calculated from samples taken from the settler effluent
streams. The efficiency of the mixers alone was determined from samples
taken through fritted glass filters immersed in the mixers (Sec. 4.0).
Equilibrium data were obtained by taking samples of dispersion from the
mixer and sh,iking for 10 min in separatory funnels.
 -55-
Table 8.1. Stage Efficiencies of Climax Mixer-Settlers

Uranium Concentration,a g/liter Efficiency, $

Stage Settler Mixer-
No. Feed Equil. Mixerb Effluent Mixer Settler

Extraction Circuit

1
2
3
5 02
1.62
0.20
..
1.35
0 072
0 010
2.10
0.40
0.053
1.62
0.20
0.023
80.5
78 7
77.4
93 00
91.6
93 -2
Stripping Circuit

1 3 02 5 02 " 5 42 .. 100
2 5 92 2*7 " 3.1 I 84
3 3.1 0.08 0.18 P 97
?Jranium concentration in aqueous in extraction circuit and in solvent
in stripping circuit.
bAqueous sample taken through fritted glass filter immersed in mixer.

In the extraction circuit the efficiency of three adjacent stages

was nearly constrantover a wide range of uranium concentrations. Tne
over-all efficiency of each mixer-settler was significantly greater than
that of only the mixer because some extraction occurred during phase
separation. The residence time of the dispersion in the mixer was 1.2
min ,and in the settler was 1.3 min. The rate constants (eq. 7) based on
average stage efficiencies were 1.1 in the mixer and 1.7 in the mixer-
settler. The close agreement of these data with thoseobtained in small-
scale mixers (Fig. 4.6) confirms the scaleup relations based on constant
power input per unit mixer volume.

In the stripping section most of the uranium was stripped in one

stage (No. 3) where the stage efficiency was 97%. Stages 1 and 2 were
complicated by the pH being too low f o r effective stripping.

Phase Separation. The dispersion band thickness in each extraction

settler and the end strip settlers was located and measured by repeated
sampling at measured depths with EL thief sampler. Its thickness was
nearly the same in all. four extraction settlers, ranging from 5 to 6 in.
(Table 8.2). The batch primary break time (measured in 400-mL beakers)
of the dispersion dipped out of' the mixers was 57 sec, which is only
slightly more than the break time Tor sTynthetic feed used in scale-model
tests at 25OC (Sec. '7.0). Therefore the band thickness in the Climax
settlers and scale models can be compared directly without temperature
correction. The plant data fit very well on the curve for solvent-
continuous dispersion in Fig. '9.6, demonstrating valid scaleup of settlers
based on. constant flow per unit area at constant dispersion thickness.
 -56-

Tab1.e 8.2. P r o f i l e of' Climax Settlers

Layer 'Chickness, i n ,
Stage - Solvent Aqueous __p1_I Dispersion

Extraction 1 12 31 5.5
2 9 35 6.0
3 10 33 5.5
11. 9 35 5.0

S t r i p p i n g 1. 4 27
4 4 2'7

The entrainment of s o l v e n t i n t h e aqueous r a f f i n a t e w a s memiired a t

two p o i n t s i n the p l a n t . The r a f f i n a t e from s t a g e 4 was passed through a
s p a r e s e t t l . e r b e f o r e it, was discharged. Ithe average s o l v e n t entrainment
(based on t h r e e grab sainpl-es) i n r a f f i n a ' i e e n t e r i n g and l e a v i n g the spare
s e t t l e r w a s 0.37 and 0.20 ga1/1000 gal., r e s p e c t i v e l y , showing t h a t an ad-
d i t i o n a l 'no1.d time of 25 min reduced the entrainment by h a l f , The average
total inventory l o s s f o r n e a r l y two y e a r s of operation i s equivalent; t o
1.6 g a l p e r 1.000 gal of aqueous. This i n c l u d e s l o s s Bue t o entrainment
and s o l u b i l i t y i n t h e r a f f i n a t e and loaded carbonabe m d loss due t o
s p i l l a g e and evaporation. Although .the measured. entrainment; was a srm.11.
p a r t of t h e t o t a l l o s s , it may not be r e a l i s t i c because of t h e s h o r t pun
time represented by t h e entrainment sa.Iiples.

Entra?.nraent of aqueous i n t h e I.o2taed sol?-ent was 4.2 g a l per 1000 g a l

of s o l v e n t . This i s not s u f f i c i e n t t o s e r i o u s l y a f f e c t t h e operRtion of
,the strippi-ng c i r c u i t o r t h e product p u r i t y .

I n t h e strip settlers no sharp d i s p e r s i o n band ~r7a.s found, A diliut,e

di-spersion of tile s m e aqueous content as measured i n tile mixer, -10~:' io
aqueous, w a s a t t h e aqueous-solvent i n t e r f a c e 'The aqueous content of
s o l v e n t g;rad.ually decreased t o l e s s than 556 % e x - t h e -Lop of %he 20-in.
s o l v e n t Layer. This i s very similar t o the resu1.ts obtained i n s c a l e -
model s e t t l e r t e s t s with d i l u t e so1.ven.t-continuous d-ispersions ( S e c * 7.O),
where t h e f l o w capacl.ty i s li.mil;ed by entixinment and iiot by i2 d i s t i n c t
d i s p e r s i o n band.

8*2 Kerr-i:cGce O i l I n d u s t r i z s , Shiprock, I l n ble2;ico29

~_I__

Uraniuni o r e i s lenchcd wTth s u l f u r i c w i d and t h e s o l t d s a r e removcd

by c l n s s i f i e r s and thickeners zrranged f o r countercurrent i3ec3ntati oil,
The l e c c h 3-iquor from t h e t h i c k c n e r s i s t i - e n t e t i w i t h s c r a p i r o n t o reduce
t h e f e r r i c i o n coritont b e r m e uranium c x t r n c t i o n .

The solvent is 0.11 M D ~ L W Aand 3% TRP d i s s o l v c d i n a high-flash-

p o i n t kerosene (Napoleurn T(0). 'The aqueous f e e d i s not f i l t e r e d and
 -57-
contains v a r i a b l e amounts of i n s o l u b l e s o l i d s , usuo.lly less than O.5$.
Typical chemical e n a l y s i s of t h e Teed, i n [:rams p e r l i t e r , i s ; U 0.7,
V 1.1, and Fe 1.8; p H 1.4. The em" of t h e l i q u o r i s usuadly l e s s than
300 mv, so t h a t t h e i r o n and vanadium are i n reduced valence states.

Each m i x e r - s e t i l e r i n t h e e x t r a c t i o n s e c t i o n i s composed of one

16-ft-dia by 6-ft-deep wood s e t t l e r with 3, 4- by 4-ft s t a i n l e s s s t e e l
mixing t a i k supported w i t h i n t h e s e t t l e r , The a g i t a t o r i s an l&in.-dia
t u r b i n e d r i v e n by a 3-hp motor. The s e t t l e r i r e a i s 190 f t2
s e t t l e r s arc i n s t a l l e d on a grade so t h a t t h e aqueous flows by g r a v i t y
. The mixer-

and t h e s o l v e n t i s advanced by a i r - l i f t s . The i n t e r f a c e l e v e l i s s e t by

a v a r i a b l e weir on t h e aqueous discharge leg. The mixing i s aqueous-
continuous i n a l l s t a g e s except 80. 4 where solvent i s r e c y c l e d t o main-
t a i n a phase ratio of 1/1 i n t h e mixer. The temperature i s b o C .

I n t h e s t r i p p i n g s e c t i o n each m i x e r - s e t t l e r i s comprised of a 4- by
4-ft mixer followed by an 8-ft-ctia cone-bottom s e t t l e r . The s o l v e n t flows
by g r a v i t y and t h e aqueous s t r i p s o l u t i o n by pump. The mixing i s solvent-
continuous i.n both s t a g e s . Steam-heating c o i l s a r e i n s t a l l e d i n t h e
mixers and t h e temperature i s maintained a t 45oC.

Uranium P r o f i l e . The p r o f i l e of uranium concentrations i n both

phases from each s t a g e i s shown i n Fig. 8.3. I n t h e e x t r a c t i o n s e c t i o n
t h e uranium concentration i n %he aqueous phase w a s reduced from 0.68 'to
l e s s t h a n 0.001 g l l i t e r i n f o u r s t a g e s , giving 33.976 uranium recovery.
The e x t r a c t i o n was e s s e n t i a l l y complete i n t h r e e stages, t h e f o u r t h s t a g e
serving as r e s e r v e capacity. I n t h e s t r i p p i n g c i r c u i t the profile shows
t h a t v i r t u a l l y a l l t h e uranium i s s t r i p p e d i n t h e second s t a g e . S t r i p p i n g
does not occur i n t h e f i r s t stage because t h e flow of sodium carbonate t o
t h e c i r c u i t i s c o n t r o l l e d t o maintain t h e pH of t h e loaded s t r i p a t less
t h a n 7.5, which i s t o o low f o r e f f e c t i v e s t r i p p i n g .

Stage E f f i c i e n c y . The s t a g e e f f i c i e n c i e s of t h e m i x e r - s e t t l e r s were

c a l c u l a t e d from samples tn;ken from t h e s e t t l e r e f f l u e n t streams and equi-
l i b r i u m values obtained by shakeout of samples dipped from tine nixers.
The e f f i c i e n c y of' t h e m i x e r - s e t t l e r s i n t h e e x t r a c t i o n c i r c u i t rLulged
from 89 t o 99%. The measurements were complicated by f l u c t u a t i n g r e c y c l e
w i t h i n each m i x e r - s e t t l e r , which caused r<apid changes of phase r a t i o
w i t h i n t h e mixer. Therefore, although t h e s t a g e e f f i c i e n c y i s a p p a r e n t l y
g r e a t e r than 90% most of t h e time, t h e data are not u s e f u l for checking
scaleup f a c t o r s . Attempts t o neasure t h e e f f i c i e n c y of t h e mixers alone
by sampling t h e dispersed phase with f r i t t e d f i l t e r s were u n s u c c e s s f b l b e -
cause t h e d i s p e r s i o n w a s s o f i n e t h a t t h e f i l t e r s dia not give good
s e p a r a t i o n of t h e phases,

Phase Separation. The d i s p e r s i o n band t h i c k n e s s i n each s e t t l e r i n

t h e e x t r a c t i o n c i r c u i t i s shown i n Trzble 8.3. The f i r s t t h r e e s t a g e s
were operated w i t h a,yueous-continuous d i s p e r s i o n a t an A/O phase r a t i o of
9/1 and t h e f o u r t h s t a g e w a s solvent-continuous with s o l v e n t recycled by
a c e n t r i f u g a l pump to maintain a phase ro.tio of 1/1 Tn t h e mixer. Phase
-58-

UNCLASSIFIED
0 R NL -LR- DWG 4-7797
 -59-

Table 8.3. Profile of Shiprock Extraction Settlers

Stage Continuous A/O Phase Lsyer Thickness, in.

No * Phase Ratio Aqueous Solvent Dispersion

1 Aqueous 9/1 39 3 18
2 Aqueous 9/1 39 5 16
3 Aqueous 9/1 41 8 11
4 Organic 1/1 45 9 6

separation was markedly affected by the type o f dispersion, as shown by a

band thickness of 6 in. for solvent-continuous compared. to I1 to 18 in.
for aqueous-continuous. The dispersion band deptn was greatest in the
first stage settler; in fact, the dispersion periodically overflowed with
the loaded solvent into the stripping circuit. Most of the dispersion in
the settler was a coarse emulsion consisting of a relatively large volume
of solvent dispersed in aqueous, The einulsion w a s easily broken by porn-
ing it into a mixer containing solvent and thereby inverting it to a
solvent-continuous dispersion. The cause of the emulsion is believed to
be decomposition products of certain vegetable gums used for flocculation
of ore slimes in the thickener circuit. The difficulty is avoided by us-
ing synthetic flocculating agents or by operating with solvent phase con-
tinuous as was done in the fourth stage.

Because of the emulsion difficulty, only the data for solvcnt-

continuous dispersion in the fourth stage cczn be used for checking the
scaleup relations. The batch break time of 400-ml samples dipped from
the mixer was 40 sect which is only slightly less than that for the sys-
tem used. in the scale-model settlers; consequently the band thickness can
be compa,red directly with that measured in the scale models. The good
agreement of the plant data with Yne curves shown in Fig. 7.6 confirms the
scaleup relations based on constant dispersion thickness at constant flow
rate per unit settler area.

The entrainment of solvent in the aqueous raffimte w a s measured in

grab smples taken from the No. 4 settles discharge. The entrainment in
eight samples was less than 0.1 ga1/1000 gal. Plant recorda for April
1958 o f daily composites of the raffinate showed an average entrainment
of 0.2 gal/1000 gal except for two days vhen emulsions were encountered
and the entrainment was as high as 1.5 gal/l000 gal. The total inventory
loss of solvent since plant startup has been equivalent to 0.8 ga1/1000
gal. This includes l o s s due to entrainment, solubility, spillage, and
evaporation. When no spillage was recorded the inventory loss was less
than 0.5 ga1/1000 gal.

In the strip circuit no sharp disperoion band was observed in the

settlers. Primary break time of dispersion dipped from the mixers was
less than lmin. The entrainment of aqueous in the stripped solvent was
 -60-
4.0 ga1/1000 g a d which was eqiiivalent t o 0.2 g of uranium per l i t e r of
solvent e n t e r l n g the r a f f i n a t e s t a g e OS -the e x t r a c t i o n c i r c u i t , However,
because sf the high -uranium extractLon c o e f f i c i e n t this d i d not cause high
10ss of uranium i n t h e r a f f i n a t e ,

1, A. D. Ryon and K. 0. Johnsson, "Progress Report of: Process Tes'L

Section f o r July 1956, I t ORidz-22l3; August 1956, OR1NL-2214; September
1956, ow&-2215.
2, K. B, Urovn, C . F. Coleman, D. J. Crouse, and A. D. Ryon, "Progress
Report on Raw Materials f o r Feb-mary 1957," ORNL-2269; March 1957,
ORNL-2306;A p r i l 1957, ORKL-2346; May 1957, 01-w~-2366; June 1.95'7;
o m ~ - 2 3 8 0 ; J u l y 1957, 01.:~~-2388;
August 1957, OmL-2399; September
1957, OI-WT.,-2443; October 1957, OlU&-2451; November 1957, ORNL-2466 e
3. S. A. MLllcr and C . A. Maim, "Agitation of Two-phase Systems of
Immiscible Liquids," Trans. A.P.Ch.X., 40: 709 (1.944).
4. A. W. Plynn and R. X m Treybal, "Liquid-Liquid E x t r a c t i o n i n
Continuous-flow Agitated l3xtractor.s , I t A . 1 .Ch.E.J., 1: 324 (1955).

5. A. E. Karr and E. G. ScheLbel, "Mass 'Transfer Between immiscible

Liquids i n Continuous Flow i n an Agikated Cha.mber," Chem, Eng. Prog.
Symposiim S e r i e s No, 10, 50: 73 (19>4).

6 * R. E. 'Treybal, "Liquid Extraction," p. 2?[6, McGraw-iJiL1, New York,

1951.
'I. C. A. B l a k e , K. B. Rrotm, and C. F. Coleman, "Thc Xxtraction and
k c o v e r y o f Uranium (and Vanadium) from Acid Liqiiors w i t h Di(2-
ethylhcxy1)phospl~oricAcid and Some Other Organophosphorus Acids, '*
ORlK-1903 (1955;).
8. C. A. Blake, D. J. Crouse, C. F. Coleman, K. 13, Rrown, and A. D,
Kelmers, "Pjl'oqess Report;: Further Sbudics of t h e Dia-lkylphospharic
Acid E x t r a c t i o n (Dapex) Process f o r Uranium, I' 01ii11TT,-2172 (1956)

9. K. B. Brown, C. F. Coleman, D. J. Crouse, C, A. El,d.se, and A. D.

Ryon, "Solvent Extraction Processing of Uranium and Thorium Ores, "
P/rOg, Proc. '2nd I n t e r n a t l , Conl". on Peaceful Uses of Atomic Jhergy,
Val. 3, p. 472, U.N., New York, 1-958.

1Q. K. 5 . Brown C . F. Coleman, "Solvent E x t r a c t i o n in. Ore ProCessl.ng2"

Prog, Muclear Energy, S e r i e s 111, P'roccss Chemj-stry, 2: pp. 3-34,
Pergamon Press, New Hork, 1958.
 -61-
11 C. A, Blake, D. E. Horner, and J. M. Schmitt, "Synergistic Uranium

.
Extractmts : Combination of Neutral Organophosphorus Compounds with
Dialkylphosphoric Acids, I t ORNL-2259 ( 1959)

12. C. F, Baes, Jr., R. A. Zingaro, 'and C, F. Coleman, "The Extraction

of Uranium( VI) from Acid Perchlorate Solutions by Di( 2-ethylhexy1)-
-
phosphoric Acid in n-IIexane," J. Phys. Chem., 62: 129 (1958),

13 C, F, Baes, Jr., "An Isopiestic Investjgntion of Di( 2-ethylhexy1)-

-
phosphoric Acid and Tri-n-octylphosphine Oxide in
Om-273'1 ( 1959)
14. R. B. MacMullin and J, blebes, Jr., "The Theory of Short-circuiting
in Continuous Flow Mixing Vessels in Series and the Kinetics of
Chemical Reactions in Such Systems," Trans. A.I.Ch.E., 31: 409
(1935).
15
I,4

Practice," Chem. Eng. Prog., 49: 161 (1953).

-
J. H. Rushton and J. Y. Oldshke, "Mixing Present Theory and

16 . D. S , Laity and R, E. Treybal, "Dynamics of Liquid Rgi-tation in the

Absence of an Air-Liquid Interface," A.I.Ch.E.J., 3: 176 (1757).
17 W. A. Rodger, V. G. Trice, Jr., and J. H. Rushton, "Effect of Fluid
Motion on Interfacial Area of Dispersions," Chem, Eng, Prog., 52:
515 (1956).
18. S. Glasstone, K. J. Laidler, and H. Eyring, "The Theory of Rate
Processes," p , 400, McGraw-Hill, Nev York, 1941.

19. J. H. Rushton, "How to Make Use of Recent Mixing Developments," Chem.

Eng. Prog., 50: 587 (1954).
20 V. G, T r i c e , Jr., Argonne National Laboratory, private communication,
1957
21. T. Vermeulen, G. M. W i l l i a m s , and G. E. Langlois, "Interfacial Area
in Liquid-Liquid and Gas-Liquid Agitation," Chem. Eng, Prog. 51: ,
85F 0955).
22. J. R. Davidson, A. C, Schafer, Jr., and W. 0. Haas, Jr., "The
Appl.ication of Mixer-Settlers to the Purex Process," Symposium on
the Reprocessing of Irradiated Fuels Held at Brussels, Belgium,
May 20-25, 1957, p . 130, Book 1, TIP-7534.

23 J. C . Bresee, "Progress Report for February 1956," ORNL-CF-56-2-1,%.

24, H. 5. Groh, "Removal of Silica from Solutions of Nuclear Fuels,"
DP-293, June 1958.
25, T. J. Colven, Jr., "Ytixer-Settler Developmefit; Operating C h a r a c t e r i s t i c s
of Large Scale Ni x e r - S e t t l e r s , I t DP-140, October 1956"

26. K. R. Brom, "Progress Report on Haw M a t e r i a l s for necclnher 1.957,"

0~~2h86.

2Te -
>I. B. Hart, "Refinery Waste TX s p o s a l Four F a c t o r s Are Iilajor
Controls i n Desi ga of m Economical O i I - I J a t e r Separator, 'I Petroleum
Processing, 2: 282 ( A p r i l 1-91t7).
28* R. C. Toerper, "'i'he Applicztion of Solvent Extractior, in Climax
U r a n i u m Company' s P l a n t , I t presented a t Nati.onal Western VliaiiIg
Conference, Denver, Peb e 7, 1957.

29* bJ. C. Hazen, "Solvent Extrackion of U r a r i i u m a t Shiprock, New Mexico,

P l a n t oZ Kerr-McGee O i l Tm.Iustries, 'I presented a t R i m Meeting,
New Orlsans, Feb. 27, 1957.

10.0 WPNVDIX

1.0 .I Nomenclature
e

R - Aqueous flow ratx, g a l / r i n

A' - I n t e r r a c i a l area, cm2
a - I n t e r f a c i a l . surface area, per u n i t volurnt. of d i s p e r s i o n , c&/cm3
c - Uranium concentration i n aqueous after c o n t a c t tiiiw, t, g / i i t e r
C, - I n i t i a l uranium concentration i n aqueous, g / J i t e r
Ceq - 1Scliiilibriu.m uranium concentration i n aqueous, e/li.te:e
D - Turbine diameter, i n .
E - stage e f f i c i e n c y , 4
g . Gravity canvers-ion factor
- 'Turbine constant,
- Rate constant, cm/min
K

- E f f e c t i v e r a t e constant,
k
ka min" 1
TT - Turbine speed, rpm
o - Solvent flow rate, gal/min
T - Pover i n p u t t o mixer, hp
- Aqu.eous volume i n mixer, gal.
--
R
T Mixer diameter, in,
t Contact time i n mixer, min
V - Mixer volume, gal-
p - Mean density- of d i s p e r s i o n , g/ml

10"2 De.tsiled. Data Tables

D e t a i l e d d a t a Prom t'ne bEtcsh and conti-nuous mixing tc.s%sare given

i n Tables 10.1 and 10.2
 Table 10.1. Batch irsaniux &traction Tests

Power
Input,
Mixer Turbine hp/ Uranium Concentration, g/liter
Dia, Dia, Speed, 1000
in. in. r p m gal 0 sec 5 sec 10 see 20 see 30 sec 45 see 60 sec 75 sec 120 see 240 sec 480 sec shown = 1/3
System A
6 3 262 2.5 5;20 3.60 3.35 2.80 2.40 1.88 1.56 1.25 0.74 0.32 0.24 0.51 0.64
350 5.9 5.20 3.20 2.70 2.05 1.62 1.16 0.09 0.69 0.38 0.25 0.24 0.83 1.04
524 20 5.20 2.25 1.83 1.20 0.89 0.53 0.36 0.26 0.27 0.23 0.24 1.48 1.85
767 67 5.20 1.30 1.31 0.73 0.47 0.29 0.26 0.24 0.25 0.25 0.28 2.36 2.95
1170 220 5.20 1.55 0.85 0.47 0.29 0.25 0.24 0.25 0.25 0.26 0.27 3.70 4.63
12 4 323 2.5 5.20 - 3.25 2.45 1.89 1.52 1.07 - 0.47 0.26 0.25 os% 0,s
-
1

-
~

W
430 5.9 5.20 1.71 1.27 0.87 0.64 0.46 0.26 0.23 0.25 1.22 1.22 t

647 20 5.20 - 1.55 0.90 0.51 0.41 0.29 - 0.24 0.24 0.25 1.82 1.83
970 67 5.20 - 0.92 0.50 0.35 0.27 0.24 - 0.23 0.24 0.27 2.92 2.92

20 6 5.9 5.40 - 3.15 2.20 1.52 1.02 0.52 0.31 0.25 0.25 1.10 1.07
-
370 0.70
4 1140 24 5.40 2.70 1.16 0.73 0.44 0.32 0.27 0.24 0.24 0.26 1.82 1.57
6 1140 170 5.40 1.50 0.93 0.45 0.29 0.24 0.22 0.24 0.26 0.27 0.30 3.60 3.50
System 13
6 3 262 2.5 1.16 0.89 0.83 0.75 0.63 0.57 0.38 0.23 0.16 0.59 0.74
350 5.9 1.16 0.78 0.67 0.61 0.49 0.43 02.9 0.19 0.16 0.85 1.07
524 20 1.16 0.71 0.62 0.50 0.41. 0.34 0.22 0.17 0.16 1.15 1.4L
787 67 1.16 0.52 0.41 0.32 0.26 0.23 0.17 0.16 0.17 1.97 2.46
1170 220 1.16 0.52 0.38 0.30 0.24 0.20 0.16 0.18 0.19 2.35 2.94
 Table 10.1 ( continued)

- - ~- ~ ~~
- __ ~
~-
Power
~

Iripu"; ,
Mixer TurSine h?/ Ur,ziu;n concentrztion, g/liter kaj ,nk-&,
D i s , D i a , Speed, LOO3 4t D 1 At D T
i n . in. rpm gal 0 sec 5 sec 10 sec 20 sec 30 sec 45 Eec 60 sec 75 sec 120 sec 240 sec 480 sec shown = 1/3

System B (continued)
12 4 323 2.5 1.16 0.79 0.70 0.60 0.51 0.42 0.29 0.20 0.17 o.S& 0.88
430 5.9 1.~6 0.68 0.58 0.49 0.40 0.34 0.22 0.17 0.17 1.11 1.u.
6k7 20 1.i6 0.59 0.49 0.40 0.33 0.28 0.19 0.19 0.19 1.43 1.43
970 67 1.16 0.51 0.41 0.32 0.26 0.22 0.18 0.18 0.20 1.97 1.97
il

20 6 290 2.5 1.25 - 0.93 3.82 0.58 0.48 0.19 0.i2 0.i2 1.00 0.95
Ch
-f
3 1143 5.8 1.16 - - - ,3.42 0.34 0.14 0.11 0.12 1.h 1.15
6 1143 10 1.27 0.84 0.65 9.52 0.39 0.30 0.16 0.11 0.12 1.29 1.25
4 1140 24 1.16 0.58 0.42 0.31 0.20 0.15 0.10 0.10 0.12 2.06 1.77
5 1140 73 1.16 0.56 0.40 0.26 0.18 0.14 0.09 0.09 0.13 2.32 2.10
6 1140 170 1.15 0.50 0.35 0.23 0.16 0.12 - - 0.13 2.79 2.71

12 2 2050 20 1.16 0.52 0.4i 0.3; 0.26 0.23 0.17 3.S 0.3 1.92 -
3 io40 20 1.16 0.52 0.39 0.34 0.28 0.24 0.18 0.17 0.18 1.77 -
Li. 647 20 1.i6 0.59 0.49 0.40 0.33 0.28 0.19 0.19 0.19 1-43 -
6 329 20 1.16 0.69 0.55 0.45 0.37 9.31 0.22 0.17 0.18 1.28 -
8 204 20 1.16 0.76 0.63 0.53 0.45 0.39 0.26 c.21 0.2~ 0.97 -
 Table 10.2. Continuous Flow Urmim Extraction Tests
System A

Mixer: 6-in. with 3-in. turbine (4 blade)

A/@ phase r a t i o : 1/1
Aqueous feed: 5.3 g U/liter; a t e q u i l i b r i m , 0.20 g U / l i t e r

Powes U i n Raffinate, 1

Turbine Input, g/liter Efficiency, $I ka, min'-'

Run Speed, hp/lOOO Effluent Calc. from Fritted Fritted Calc. a t
NO. r3?m gal Sanple F r i t t e d Teflon Effluent Teflon Teflon D/T = 1/3
Aqueous-continuous dispersion

Residence time 0.37 min; aqueous 1.0 gpm, solvent 1.0 €Pm

573 300 2.5 3.2 4.5 41.2 15.7 0.25 0.31 cIn
vi
574 400 6.O 1.9 3.7 66.7 31.4 0.62 0.78 t

575 600 20 1.3 2.9 78.4 47.1 1.20 1.50

579 900 68 1.3 1.8 78.4 64.7 2.47 3-09

Residence time 0.74 min; aqueous 0.5 gpm, solvent 0.5 KPm

557
558
420
630
6.9
23
1.1
0.85 -
c 82.4
87.1 -- -- -1

91.0
559 840 55 0.66
-
-. 1 1 1

560 950 SO o .62 I 92.8 1 1

Residence time 1.5 min; aqueous 0.25 gym, solvent 0.25 g p m

543 420 6.9 0.72 c 89.8 -- 1 -.

544 630
840
23
55
0.45
-
I 95.1
96.2- -- 1

- --
1

545 0.40
-
1

546 950 80 0.38 $05

 Table 10.2 ( continued)

?over U Conc. i~ Raffina'ce,

Turbine Iaput) g/ltter Efficiency, $ ka m;in'l

Run Speed, hp/lOOO Bffluent Fritted Fritted Fritted Calc. at

No. rprn gal Szmple Glass Effluent Glass Giass D/T = 1/3
Solvent-coctinuous d l s p e r s i o n

Residerxe time 0.37 min; x p e o u s 1.0 gpm, solvent 1.3 g p n

5 76 300 2*5 3.2 4.7 41.2 11.8 0.18 0.23

400 6.0 2.3 4.6 58.8 i3.8 0.22 0.229
78.4 0.56
1
581 600 20 1.3 3.8 29.4 0.70 a
cp\

583 900 68 0.93 2.9 85.7 Q.1 1.23 1.50 B

Residence tirrie 0.82 r5n; aqueous 0.45 gpm, s o l - r e n t 0.1.;5gpm

564 420 6.9 1.1 2.6 82.4 53 00 0.68 0.86

565 630 23 0.72 2.o 89.8 64.7 1.12 1.40
566 840 55 0.55 i.6 92.4 72.6 1.51 2.02
5-57 4'53 9Q 0.62 1.5 92.2 74.5 i.80 2.25

55i !+2c 6.5 0.66 2.2 91.0 6c.G 0.52 0.65

552 63c 23 0.53 1.6 93.5 72.6 0.38 1.10
553
554
840
950
55
86
.
0 %2
0.43
1.3
1.3
95.7
95.L
78.4
78.L-
1.21
2.21
1.51
1.51
 Table 10.2 ( continued)

Second Pass
Aqueous feed: 1.7 g / l i t e r ; at equilibrium,0.021 &iter
Residence time: 1.5 d n
Flow rate, each phase: 0.25 e r
n
-
U Conc. in Raffinate,
~~

Power
Turbine Input, g/iiter Efficiency, $ ka, min-'
Run Speed, hp/lOOO Effluent Calc. from Fritted Fritted Calc. at
No. rpm gal Sample Fritted Sample Effluent Sample Saraple D/T = 1/3 &
7
Aqueous-continuous, Teflon sampler
590 400 5 -9 0.18 0.59 90.6 66.5 0.66 0.83
531 600 20 0.11 0.41 94.7 77.1 1.12 1.40
593 900 67 0.087 0.37 96.1 73.4 1.28 1.60

Solvent-continuous, glass sampler

588 300 2.5 0.42 0.80 76.5 54.1 0.39 0.49

584 400 5.9 0.21 0.68 58.8 61.2 0.53 0.66
585 600 20 0.14 0.48 92.9 73 -0 0.90 1.13
587 900 67 0.078 0.38 96.6 78.8 1.24 1.55
 Table 10.2 (continued)

Svsten?. E

YLxer: 6-in. with turbine (6 blade)

A/O phase r a t i o : 4/1
Aqueous - continuous dispersion

Power U Conc. i n Raffinate.

Turbine Input, g/iiter Efficiency, $ Ira, a n - 1
Ru;?
l/z
Speed,
- ~ -P ./ X O O Effluent Caic. from Fritted Fritted Calc. a t
KO. rpm gal Sample F r i t t e d Teflon Effluent Teflon Teflon D/T =
Residence time 0.17 min; aqueous 4.0 a m 3 solvent 1.0 gprn

6G 0 0 1.10 1.15 - I .- -
647 262 2.5 0.94 1.11 19.3 4.9 0.24 0.30
648 350 5.9 0.81 1.06 34.3 9b8 0.51 0.64
649 524 20 0.68 0.97 46.4 16.8 1.09 1.36
650 787 67 0.59 0.89 55.1 26.2 1.67 2.09 I
cn
F)
1170 220
- 0.55 0.8k
-
58.9
-
31.4
-
r--;
03- 2.15 2.69
d!pLiL. I 0.13 0.13 "

Residence time 0.37 rniri; aqueous 1.6 a m r solvenL 0.40 gpm

634 0 0 1.06 1.16 - " " -

635 262 2.5 0.79 1.03 36.3 13.1 0.33 0.4;
636 350 5.9 0.63 0.95 51.8 20.2 0.55 0.69
637 524 2G 0.55 0.81 59.5 31. 7 1.00 1.25
635 787 57 c.50 0*7s 63.3 36.8 i.26 1.58
639
Equil.
1170
I
220
- 0.44
0.13
0.71
0.13
70.2
- -
43.2
-
1.65 2.06
-
Residence tiKe 1.5 min; aqdeous 0,bO @my soivefit 0.10 gpn

652 0 0 1.14 1.15 - - - -

653 262 2.5 0.58 0.72 56.6 43.2 0.43 C .54
65.4 350 5.9 0.46 a61 65.3 53.7 0.65 0.31
655 524 20 0.42 0.56 72.2 58.3 0.76 0.98
656 787 67 0.36 0.49 78.4 65.2. 1.06 1.33
657
EquS.
11?G
I
220
- 0.31
0,14
0.43
0.14 -
83.6
-
71.2 1.39
- 1.74
-
 Table 10.2 ( continued)

Power U Conc. i n Raffinate,

Turbine Input, g / l i t er Efficiency, $ ka,
RUa S-rseed,
.. h~/1000 Effluent Calc, from Fritted Fritted Calc. a t
D/T = l / 3
--I

No. rpn gal Sample F r i t t e d Teflon Effluent Teflon Teflon

Residence t i m e 2.5 min; aqueous 0.24 a m , solvent 0.06 a m

G 40 0 0 1.07 1.15 - - -
641 262 2.5 0.42 0.50 72.3 56.3 0.42 0.53
6 42 350 5.9 0.32 0.49 81.6 65.2 0.60 0.75
61~3 524 20 G.31 0.45 83.0 68.6 0.72. 0.89
644 787 57 0.28 0.40 65 09 74.1 0.92 1.15
645
Equil. -
1170 220
- 0.23
0.13
0.32
0.13 -
90.3
-
8i.3
-
1.40 1.75
-
Residence time 4.8 min; aqueous 0.12 a m , solvent 0.03 g p m I
cn
593 0 0 - 1.26 - - - - Y
659 262 2.5 0.41 0.53 79.3. 66.9 0.34 0.43
660 350 5.9 0.33 0.46 66.5 73.6 0.47 0.59
661 524 20 0.31 0.42 88.8 77.9 0.59 0.74
662 737 67 0.27 0.34 92.1 84.5 0.92 1.15
553 1170 220 0.23 0.27 95.8 91.1 1.72 2.15
Residence time 1.5 min; aqueous 0.24 gpm, solvent 0.24 gym*
671 0 0 - 1.21 - - - -
672 262 2.5 0.57 0.66 61.1 53 -9 0.39 0.49
673 350 5.9 0.4j 0.53 72.0 65 .O 0.64 0.80
674 524 20 0.34 0.43 82.9 76 .2 1.06 1*33
675 737 67 0.28 0.34 88.2 84.5 1.8i 2.26
676 1170 220 0.27 0.32 92.5 86.4 2.11 2.64
3c
A/O phase satic = 1/1, organic continuous aispersion; f r i t t e d glass sampler used.
 Ta-bie 10.2 (continued)

,%xer: 2-2 i n . with bin. t u r b i n e (6 blzde)

Power U Conc. in Raffina-te.

Turbine In?xZ g/liter Efficiency, k z j min-1
RUl SpeeZL, ;lp/i000 Effhent Calc. from Fr itte& Fritted
No. mrn gal Sznple Fritted Teflon Efflmnt TeTion Teflon
Residence time 2.2 min; aqueous 2.1 @my solvent 0.52 a
m
663 0 0 1.25 I - . ..
664 323 2.5 0.42 0.60 74.8 58.6 ci.53
665 $30 5.9 3.37 0.52 79.3 55.8 0.7;
666 647 20 0.32 0.38 83.8 78.5 1.35
667
Equil.
970
.. 67
- 0.29
0.14
0.36
0.111
86.5
- -
80.8
-
1.56

Zesidence "Lime 5.0 fin; aqueous 0.92 a m , ?solvent 0.23 gpm

667 0 0 1.21 I - - -
668 323 2.5 0.26 0.39 66.5 76.0 0.51
669 430 5.9 0.27 0.32 87.4 83.0 0. '78
670 6k7 20 0.24 0.27 90.2 37.6 1.13
671 970 67 93.9 88.8
Epil. " .
0.21
0.1L
0.26
Q.lk - 0
1.27
m
 Table 10.3. Iron and Vanadium Batch Extraction Rate Data

Mixer Turbine Input, A/O Concentration i n Aqueous, & i t e r ka, a n n 1

D i a , DDia, Speed, hp,hOOO Phase 0 10 20 30 60 120 240 480 960 A t D/T Calc. a t
in. in. rpm gal Ratio sec sec see sec see see see sec see sho-m 9/92 = l/3

Iron( 1111 Extraction

6 3 262 2.5 4/i 0.22 0.22 0.21 0.21 0.20 0.19 0.17 0.15 0.13 0.070 0.088
524 20 4/1 0.22 0.21 0.20 0.20 0.19 0.18 0.16 0.13 0,11 0.092 0.U
1170 220 4/l 0.22 0.20 0.19 0.19 0.17 0.16 0.13 0.11 0.07 O,i4 0.17
4/1 0.20 0.19 0.18 0.16 0.12 0.08 0.04 0.01 0.11 0.14 1
524 20 0.22 4
524 20 i/i* 0.22 0.19 0.16 0.18 0.15 0.12 0.06 0.04 9.01 0.11 0.14 ‘f
Vanadium( IV) Extraction

3 262 2.5 4/1 6.94 0.89 0.85 0.81 0.71 0.60 0.49 0.43 - 0.43 0.54
---
6
524 20 4/1 0.94 0.78 0.74 0.70 0.60 0.48 0,43 0.44 0.76 0.95
1170 220 4/1 0.94 0.72 0.66 0.60 0.51 0.46 0.46 0.50 1.51 1.89
0.99 3.62 0.49 0.40 0.26 0.18 0.17 0.20 0.97 1.20
524
524
20
20
1/1
l/l* 1.00 0,55 0.46 0.39 0.26 0.19 0.18 0.20 - OD97 1.20
4 647 4/i 0.94 0.76 0.70 0.66 0.55 0.46 0.42 O.k4 . 0.89 0.89
12
l2 4 970
20
67 4/1 0.94 0.71 0.65 0.59 0.50 0.43 0.42 0.45 - 1.26 1.2G

*Solvent-continuous dispersion.
 Table 10.4. Contjnuaus-flow U r a n i u m Stripping Data
Mixer: 6 - i n , dia, 3-in, turbine
Solvent: 0.16 M DEIXPA, 35 g TRT l i t e r
-
S t r i p p i n g agentT l.0 M Na.2CO 33 (5% excess
O/A phase r a t i o : 5/1

Solvent Cone Turbine

Kun
.
Flow Rates, g p m g/l:ter Speed, Efficiency,
No Solvent Aqueous In out TPm c

First Stage

603 0.43 0.083 5.4 0.62 200 93

604 0.43 0.083 5.4 0.36 300 98
405 0.43 0.083 5 .4 0.35 400 99
606 0.43 0 * 083 5.4 0.34 600 99
611 1.8 0.33 5.4 1.71 300 73
612 1.8 0.33 5.4 1.25 400 82
413 1,8 0.33 5.4 0.60 600 95
614 1.8 0.33 5.4 0.42 900 98
Second Stage
607
608
0.43
0.43
0 .
079
0.079
0.43
0.43
0.042
0.022
208
300
94
99
609 0.43 0.079 0.43 0.021- 400 99
610 0,43 0 079 0.43 0.021. 600 99
615 1.7 0.34 1.0 0.086 300 96
616 1.7 0.34 1.0 0 066 400 98
617 1-7 0-34 1.0 0.058 600 98
618 1.7 0.34 1.0 0.058 goo 98
 - 73-
Ofm-2951
-
UC 10 Chemistry- Separation Proce s se s f o r
Plutonium and Uranium
‘ED-4500(15th ed.)
INTERNAL DISTRIBUTION

1. C. E. Center 63. E. D. Arnold

2. Biology Library 64. C. E, Guthrie
3. Health Physics Library 65. J. W. Ullmam
4-5. Central Research Library 66. X. B. Brown
6 . Reactor Experimental 67. R. S. CocEL1.ehm11
Engineering Library 68. R. G. Wymer
7-26. Laboratory Records Department 69. J. W. Youngblood
27. Laboratory Records, O l w L R.C. 70. J. C. Bresec
28. A. M. Weinberg 71. J. G, Moore
29. 1,. B, Emlet (K-25) 72. K. A. Allen
30. J. P, Murray (Y-12) 73. C. F. Baes
31. J. A. Swartout 74. W. D. Arnold
32. E. X. Taylor 75. F. L. Daley
33. E. D. Shipley 76. F. J. H u r s Z ;
34.. M. L, Nelson 77. B. E. K l i m a
35-36. F. L. Culler 78. R. S. Lowrie
37. W. H. Jordan 79. F. G o Seeley
38. J. B. Adams 80, J. S. Drury
39. J. E. Frye, Jr. 81. J. C. TWhite
40. S. C. Lind 82. J. T. Long
41. G. I. Cathers 83. x. E. L,auze
42. A. Wollaender 84. R. A. McNees
k3. F. F. Blanlrenship 85. J. T. Xoberts
44. M. T. Kelley 86. J. R. FZanary
4-5. C. F. Coleman 87. W. Davis
46. R. S. Livingston 88. R. I€. Rainey
47. C . P. Keini 89. E. M. Shank
48. D. J. Crouse 90. J. 0. Blorike
49. C. E. Winters 91. C. D. Watson
50. A. D. Ryon 92. W. H. Lewis
51. D. Phillips 93. E. L a d o
52. W. K. E i s t e r 91;. W. R. Grimes
53. F. R. Bruce 95. P. M. Reyling
54. D. E. Fergnson 96. D. L. Katz (consultant)
55. 11. E. Goeller 97. C. E. Larson (consultant)
56. 13. A. Charpie 98. J. I € . Rushton (consultant)
57. M. E. Whatley 99. I. Perlman (consultant)
58. M. 3. Skinner 100. H. Worthington (consultant)
59. R. E. Blanco
60. G. E. Boyd
101, ORNL - Y - 1 2 Tecknical Library,
Document Reference Section
61, W. E. unger
62. A. T. Greslcy
 I

102. Division of Research and Development, AEC, OR0

103. IS. L. Iiazea, Farmer's Union Bldg., Denver, Colo.
104. M. E. Wadsworth, University o f Utah
l O 5 - l l 3 . E. C. Van Rl.arcom, Division o f Raw Materials, Washington
114-627. Given distribution as shown in TIU-74500 (15th ed. ) under Chemistry-
S e p a r a t i o n Processes f o r Plutonium and Uranium (75 copies- OTS)