Clea

nup

ofU

rany

lSul

fate

Solu

tion

sCl

eanu

p of

Ura

nyl S

ulfa

te S

olut

ions

Geo

rge

F. V

ande

grift

Chem

ical

Sci

ence

s an

d En

gine

erin

g D

ivis

ion

Four

Met

hods

look

ed a

t

•A

nion

Exc

hang

e of

ura

nyl s

ulfa

te c

ompl

exes

•D

irec

t Sol

vent

-Ext

ract

ion

Proc

ess

for

Ura

nyl S

ulfa

te

•Pr

ecip

itat

ion

of U

rany

l Ion

as

Ura

nyl P

erox

ide

•Co

nver

sion

to N

itra

te M

edia

Fol

low

ed b

y U

REX

Proc

essi

ng

2

Ani

on E

xcha

nge

of U

rany

l Sul

fate

Com

plex

es

•Ex

trac

tion

of u

rany

l sul

fate

from

ore

-leac

h liq

uors

is u

sed

succ

essf

ully

co

mm

erci

ally

–H

owev

er th

ese

solu

tions

hav

e di

lute

con

cent

ratio

ns o

f ura

nium

.

–Th

e lo

w c

apac

ity o

f ani

on-e

xcha

nge

resi

ns (1

-2m

eq/g

) mak

es th

is m

etho

d im

prac

tical

for

conc

entr

ated

uran

ylsu

lfate

solu

tion

conc

entr

ated

ura

nyl s

ulfa

te s

olut

ion

•Th

e so

rbin

g sp

ecie

s ar

e fe

lt to

be

UO

2(SO

4)22-

and

O2(

SO4)

34-, w

hich

will

requ

ire 2

-4

mEQ

/mm

ole

–O

r for

250

L o

f 130

g-U

/L (~

150

mol

e—30

0-60

0 eq

uiva

lent

s o

f ura

nyl i

on)

•Th

eex

trac

tion

colu

mn

wou

ldne

ed~6

00kg

ofre

sin

(bas

edon

1-2

mEQ

/g)

•Th

e ex

trac

tion

colu

mn

wou

ld n

eed

600

kg o

f res

in (b

ased

on

1-2

mEQ

/g)

•W

as re

ject

ed a

s im

prac

tical

, but

doe

s su

gges

t sol

vent

ext

ract

ion

with

alk

yl a

min

es

is a

pos

sibi

lity

3

YAJ2

Slid

e 3

YA

J2

Del

eted

the

wor

d ho

ld a

fter

nee

dYo

uker

, Am

anda

J.,

8/3/

2011

Dir

ect

Solv

ent-

Extr

acti

on P

roce

ss f

or U

rany

l Sul

fate

•Th

elik

ely

proc

essi

ngst

eps

are:

•Th

e lik

ely

proc

essi

ng s

teps

are

:–

Solv

ent e

xtra

ctio

n pr

oces

sing

to p

urify

ura

nyl s

ulfa

te fr

om o

ther

irra

diat

ed s

olut

ion

com

pone

nts.

–D

estr

uctio

nof

the

stri

ppin

gag

enti

nth

eur

anyl

sulfa

tepr

oduc

t(lik

ely

evap

orat

ion

Des

truc

tion

of th

e st

ripp

ing

agen

t in

the

uran

yl s

ulfa

te p

rodu

ct (l

ikel

y ev

apor

atio

n fo

llow

ed b

y th

erm

al d

ecom

posi

tion)

.

–Re

cons

titut

ing

the

uran

yl-s

ulfa

te/0

.1 M

-sul

furi

c-ac

id ta

rget

sol

utio

n.

–Tr

eatm

ent o

f was

te s

trea

ms

gene

rate

d fo

r sto

rage

and

fina

l dis

posa

lg

gp

4

Dir

ect

Solv

ent-

Extr

acti

on P

roce

ss f

or U

rany

l Sul

fate

•Pr

oces

s is

bas

ed o

n th

e ex

trac

tion

of u

rany

l-dis

ulfa

te a

nion

by

a so

lven

t com

pose

d of

two-

yy

ppa

rts

trio

ctyl

am

mon

ium

sul

fate

(TO

A) a

nd o

ne-p

art t

rioc

tyl p

hosp

hate

(TO

PO) d

ilute

d by

ei

ther

an

alka

ne o

r te

trac

hlor

oeth

ylen

e

•U

rani

um is

ext

ract

ed in

to th

e or

gani

c ph

ase

as U

O2(

SO4)

22-an

ion

with

two

trio

ctyl

i

id

il

hh

amm

oniu

m c

atio

ns a

nd o

ne tr

ioct

yl p

hosp

hate

•If

the

prop

er a

queo

us s

trip

ping

sol

utio

n is

cho

sen,

ura

nyl s

ulfa

te w

ill b

e st

ripp

ed a

nd th

e tr

ioct

yl a

mm

oniu

m s

alt w

ill re

mai

n in

the

sulfa

te fo

rm to

be

recy

cled

dire

ctly

to th

e ex

trac

tion

sect

ion

extr

actio

n se

ctio

n.

–Po

ssib

ilitie

s ar

e ox

alic

aci

d or

oth

er h

ydro

phili

c co

mpl

exan

ts a

s a

stri

ppin

g ag

ent.

–Th

e co

mpl

exan

t mus

t hav

e th

ree

impo

rtan

t pro

pert

ies

•fo

rms

stro

ng c

ompl

exes

with

ura

nyl i

on

•w

ill n

ot d

ispl

ace

sulfa

te in

the

orga

nic-

phas

e tr

ioct

yl a

mm

oniu

m s

ulfa

te s

alt

•ca

n be

des

troy

ed in

the

aque

ous

uran

yl-s

ulfa

te p

rodu

ct s

olut

ion

with

out

leav

ing

resi

due

in th

e so

lutio

n

•A

gre

at d

eal o

f R&

D is

requ

ired

to d

esig

n th

e pr

oces

sing

faci

lity

5

YAJ4

Slid

e 5

YA

J4

Adde

d th

e w

ord

solu

tion

to t

he s

econ

d to

last

bul

let

poin

tYo

uker

, Am

anda

J.,

8/3/

2011

Prec

ipit

atio

n of

Ura

nyl I

on a

s U

rany

l Per

oxid

e

•In

pri

ncip

al, t

he p

reci

pita

tion

shou

ld b

e st

raig

ht fo

rwar

d; th

e so

lubi

lity

prod

uct (

K sp=

[UO

22+] x

[O22-

]) fo

r ur

anyl

per

oxid

e is

1.3

x10-3

6

•H

owev

er, t

here

are

man

y fa

ctor

s th

at in

fluen

ce th

e co

ncen

trat

ions

of f

ree

UO

22+

ion

and

free

O22-

ion,

and

, the

refo

re, t

he c

ompl

eten

ess

of th

e pr

ecip

itatio

nF

lith

Hd

dth

dl

iti

thtf

thi

–Fo

r ur

anyl

ion,

ther

e ar

e pH

-dep

ende

nt h

ydro

lysi

s re

actio

ns th

at fo

rm th

e sp

ecie

s U

O2O

H1+

, UO

2(O

H) 2,

and

UO

2(O

H) 31-

and

sulfa

te c

ompl

exes

UO

2SO

4, U

O2(

SO4)

22-, a

nd

UO

2(SO

4)34-

.

–Th

e fr

ee p

erox

ide-

ion

conc

entr

atio

n is

als

o ef

fect

ed b

y th

e pH

, due

to fo

rmat

ion

of th

e w

eak

acid

s H

2O2

and

HO

2-

–Th

e re

lativ

e co

ncen

trat

ions

of u

rany

l-sul

fate

com

plex

es a

re a

lso

rela

ted

to p

H th

roug

h th

e eq

uilib

ria

of s

ulfa

te io

n w

ith H

SO4-

and

H2S

O4

–Fu

rthe

r co

mpl

icat

ions

to th

e pr

ecip

itatio

n ar

e th

at p

erox

ide

ion

can

also

form

com

plex

es

pp

pp

pw

ith u

rany

l ion

UO

2(O

2)22-

and

UO

2(O

2)34-

•La

bora

tory

test

s sh

owed

the

prec

ipita

te w

as v

ery

fine,

ver

y di

ffic

ult t

o fil

ter

or

cent

rifu

ge, a

nd, t

here

fore

, diff

icul

t to

was

h an

d re

cove

ry.

–N

ot a

ccep

tabl

e fo

r in

a p

rodu

ctio

n se

ttin

g

6

Conv

ersi

on t

o N

itra

te M

edia

fol

low

ed b

y U

REX

and

Reco

nver

sion

to

Sulf

ate

Med

ia

•St

eps

–A

dditi

on o

f sol

id B

a(N

O3)

2to

the

irra

diat

ed u

rany

l-sul

fate

sol

utio

n in

a s

tirre

d ve

ssel

; add

ition

rate

, st

irri

ng s

peed

, and

tem

pera

ture

mus

t be

set t

o op

timiz

e th

e m

orph

olog

y an

d si

ze o

f the

cry

stal

s fo

rmed

to a

llow

faci

le fi

ltrat

ion.

–Pa

ssin

gth

esl

urry

into

afil

trat

ion

syst

emto

colle

ctan

dw

ash

the

prec

ipita

te(m

inim

ize

uran

ium

Pass

ing

the

slur

ry in

to a

filtr

atio

n sy

stem

to c

olle

ct a

nd w

ash

the

prec

ipita

te (m

inim

ize

uran

ium

lo

sses

).

–U

REX

proc

essi

ng o

f the

filtr

ate.

–Ru

n U

-pro

duct

sol

utio

n th

roug

h an

ani

on-e

xcha

nge

colu

mn

to re

mov

e pe

rtec

hnet

ate

and

iodi

de.

–Co

ncen

trat

ion

and

deni

trat

ion

of th

e so

lutio

n to

form

UO

3.

–D

isso

lutio

n of

UO

3 in

sul

furi

c ac

id (

som

e hy

drog

en p

erox

ide

may

be

requ

ired

if al

l ura

nium

is n

ot in

th

e VI

oxi

datio

n st

ate)

.

–Re

cons

titut

ing

the

uran

yl-s

ulfa

te/0

.1 M

-sul

furi

c-ac

id ta

rget

sol

utio

n.g

y/

g

–Tr

eatm

ent o

f was

te s

trea

ms

gene

rate

d fo

r st

orag

e an

d fin

al d

ispo

sal

•A

ll pr

oces

s st

eps

are

used

com

mer

cial

ly a

nd w

ell u

nder

stoo

d–

Min

imum

R&

D is

requ

ired

to d

esig

n pr

oces

sing

faci

lity

7

Targ

et-S

olut

ion-

Clea

nup

Flow

shee

tSp

ent u

rany

l-sul

fate

targ

et s

olut

ion

Ba(N

O3)

2

Conv

ert

(UO

2)SO

4to

U

O2(

NO

3)2

solu

tion

(stir

red

vess

el)

Filte

r an

d w

ash

URE

X

Sulfa

te p

reci

pita

te

Filtr

ate

Raff

inat

e(t

o w

aste

)

Slur

ry

Ani

on

Ther

mal

Co

ncen

trat

ion

by

pp

(to

was

te)

Elue

nt

U, T

c, a

nd I

Prod

uct

exch

ange

Den

itrat

ion

yev

apor

atio

n

Tcan

d I

(to

was

te)

Elue

nt

UO

3/U

3O8

Trea

t was

te s

trea

ms

gene

rate

d fo

r sto

rage

and

fina

l dis

posa

l.D

isso

lve

in

sulfu

ric

acid

(h

ydro

gen

Adj

ust

uran

ium

co

ncen

trat

ion

(to

was

te)

(hyd

roge

n pe

roxi

de)

conc

entr

atio

n an

d pH

8

Reco

nsti

tute

d ur

anyl

-sul

fate

targ

et s

olut

ion

Conv

ersi

on f

rom

Sul

fate

to

Nit

rate

Med

iaTh

dditi

flid

B(N

O)

tth

tSH

INE

Tt

lti

illd

lft

•Th

e ad

ditio

n of

sol

id B

a(N

O3)

2to

the

spen

t SH

INE

Targ

et s

olut

ion

will

dro

p su

lfate

co

ncen

trat

ion

to le

vels

bel

ow o

f con

cern

to U

REX

proc

essi

ng

•To

tal s

ulfa

te in

the

feed

can

be ≤0

.01M

with

no

sign

ifica

nt e

ffec

t•

Expe

rim

enta

l res

ults

ver

ify m

odel

s pr

edic

tion,

but

the

solu

tion

mus

t be

heat

ed to

incr

ease

p

yp

solu

bilit

y of

Ba(

NO

3)2

for

com

plet

e co

nver

sion

9

URE

X Pr

oces

s•

The

URE

X so

lven

t ext

ract

ion

proc

ess

is a

mod

ifica

tion

of th

e co

mm

erci

al P

URE

X pr

oces

s

–M

odifi

ed b

y th

e ad

ditio

n of

ace

tohy

drox

amic

aci

d (A

HA

) to

the

scru

b fe

ed

AH

Ai

ill

ilbl

hi

lhi

hid

l–

AH

A is

a c

omm

erci

ally

ava

ilabl

e ch

emic

al w

hich

pro

vide

s se

vera

l ad

vant

ages

URE

X pr

oces

s

•Pu

and

Np

do n

ot e

xtra

ct d

ue to

a c

ombi

natio

n of

co

mpl

exat

ion

and

redu

ctio

nby

AH

Aco

mpl

exat

ion

and

redu

ctio

n by

AH

A

•Fi

ssio

n pr

oduc

ts th

at a

re tr

oubl

esom

e to

PU

REX

(Zr,

Ru, M

o)

are

also

com

plex

ed b

y A

HA

and

, the

refo

re, n

ot e

xtra

ctab

le

•Be

caus

e of

thes

e fe

atur

es, U

REX

need

s on

ly o

ne c

ycle

,

yy

com

pare

d to

thre

e fo

r PU

REX

for

prod

ucin

g hi

gh p

urity

ur

aniu

m in

hig

h yi

eld

•O

n st

andi

ng (e

spec

ially

with

hea

t) in

nitr

ic a

cid

solu

tions

, A

HA

illd

iid

di

idA

HA

will

dec

ompo

se to

ace

tic a

cid

and

nitr

ous

acid

•Th

e U

REX

proc

ess

was

dev

elop

ed a

t Arg

onne

Nat

iona

l Lab

orat

ory

unde

r th

e D

OE

NE

AFC

I/G

NEP

pro

gram

.It

hb

dt

td

tth

ilt

ltA

dS

hRi

Nti

l

10

•It

has

bee

n de

mon

stra

ted

at th

e pi

lot-

scal

e at

Arg

onne

and

Sav

anna

h Ri

ver

Nat

iona

l La

bora

tori

es u

sing

dis

solv

ed h

igh-

burn

-up

spen

t fue

l

AM

USE

•Th

eA

MU

SE(A

rgon

neM

odel

for

Uni

vers

alSo

lven

tExt

ract

ion)

code

also

deve

lope

dun

der

The

AM

USE

(Arg

onne

Mod

el fo

r U

nive

rsal

Sol

vent

Ext

ract

ion)

cod

e, a

lso

deve

lope

d un

der

AFC

I/G

NEP

, has

a m

odul

e fo

r de

sign

ing

URE

X flo

wsh

eet

–Co

de h

as b

een

valid

ated

–Co

de p

redi

ctio

ns w

ere

veri

fied

with

URE

X pi

lot-

scal

e de

mon

stra

tion

resu

ltsp

p

–Is

use

d th

roug

hout

the

DO

E co

mpl

ex fo

r flo

wsh

eet

desi

gn/d

evel

opm

ent

•A

MU

SE h

as tw

o m

ain

mod

ules

–SA

SPE

(Spr

eads

heet

Alg

orith

m fo

r Sp

ecia

tion

and

Par

titio

ning

Equ

ilibr

ia)-

-che

mis

try

mod

ule

that

(

pg

pg

q)

yca

lcul

ates

dis

trib

utio

n ra

tios

base

d on

che

mic

ally

cor

rect

equ

atio

ns a

nd th

erm

odyn

amic

act

iviti

es

–SA

SSE

(Spr

eads

heet

Alg

orith

m fo

r St

agew

ise

Solv

ent E

xtra

ctio

n)--

mas

s ba

lanc

e m

odul

e th

at

calc

ulat

es th

e pa

rtiti

onin

g of

spe

cies

bet

wee

n th

e or

gani

c an

d aq

ueou

s ph

ases

in e

very

sta

ge b

ased

on

the

dist

ribu

tion

ratio

calc

ulat

ions

on th

e di

stri

butio

n ra

tio c

alcu

latio

ns

•A

30-

stag

e flo

wsh

eet

was

dev

elop

ed fo

r tre

atin

g a

130

g-U

/L u

rany

l nitr

ate

solu

tion

•Th

e flo

wsh

eet

pred

icts

:–

99.9

9999

9% o

f the

ura

nium

will

repo

rt to

the

U-p

rodu

ct s

trea

mp

p

–A

ll im

puri

ties

will

be

redu

ced

by ≥

107

(exc

ept

I and

Tc,

whi

ch w

ill b

e re

mov

ed in

the

anio

n-ex

chan

ge p

roce

ss)

11

The

URE

X Fl

owsh

eet

for

Peri

odic

Cle

anup

of

SHIN

E Ta

rget

Sol

utio

ns Spen

tTar

get

30%

TBP

inn-

Dod

ecan

e0.

5 M

AH

A0.

1 M

HN

O3

Spen

t Tar

get

Solu

tion.

1 M

HN

O3

0.3

M H

NO

30.

01 M

HN

O3

1 L/

min

1.69

L/m

in0.

05 L

/min

0.3

L/m

in2.

05 L

/min

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b 1

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