Journal of Theoretical and Applied Physics, 3-3, 20-26 (2009)

Solvent extraction of zirconium from nitric-hydrochloric acid solutions using

TBP
A. Sadigzadeh
1,
, S. !hehrenama
1, "
, #.
Sho$ri
1
1
Nuclear Science & Technology Research Institute, Atomic energy organization of Iran, Tehran, Iran 2
Department of Chemical ngineering, Isfahan !ni"ersity of Technology,
Isfahan, Iran
Receied! "# Au$ust 200%&Accepted! 20 'cto(er 2009&
Pu(lished! 20 )ece*(er 2009
A%stract
+olent e,traction is a co**ercial *ethod for production of pure *aterials such as -irconiu*
and hafniu* and their co*pounds fro* *ulti-co*ponent scru((er solution. /n the e,traction of
-irconiu* and hafniu* salts fro* 01'
3
, 02l, 02l'
3
and 0
2
+'
3
into neutral or$anophosphorus
co*pounds (1'P2) - such as tri(utyl phosphate (T4P)- in case usin$ *i,tures of inor$anic
acids, 1'P2 e,tracts -irconiu* and hafniu* 5ith separation factor con- sidera(ly e,ceedin$ the
correspondin$ alue for e,traction fro* solution of indiidual acids. A still hi$her separa- tion
leel is o(tained 5hen usin$ *i,ture of acids, especially those of nitric-hydrochloric acids. /n this
paper, the e,traction of -irconiu* fro* solution containin$ nitric-hydrochloric acids usin$ T4P
in treated 6erosene as diluent has (een studied. The follo5in$ para*eters hae (een inesti$ated!
effect of e,tractant, nitric-hydrochloric acids and -irconiu* concentrations, *i,in$ ti*e,
acidification of or$anic phase, the or$anic&a7ueous phase ratio and te*- perature on the e,traction
of -irconiu*.
PACs& 36.20.0-8 36.20.0(8
36.20.1$
'ey(ords# $irconium, %afnium, &traction, Tri'utylphosphate, Nitric(hy)rochloric aci)
1.
)ntroduction
9irconiu* and hafniu* co-e,ist in nature,
(ut in certain industry they *ust (e used
alone. Thus, they hae to (e separated prior
to their transfor*ation into pure *etals.
+olent e,traction is a co**ercial *ethod
for produc- tion of pure *aterials such as
-irconiu* and hafniu* and their co*pounds
fro* *ulti- co*ponent scru((er solution.
:any or$anic e,tractants hae the a(ility to
selectiely e,tract the ions dissoled in a
dilute acid solution. )eter*ination of
distri(ution factors of the ions present in the
solution is, therefore, an i*portant para*eter
in selection of the appropriate e,tractants.
:any inesti$ations hae so far (een
*ade on the solent e,traction of -irconiu*
fro* a7ueous *edia containin$ sulfuric acid
;"-2<, hydrochloric acid ;3-6< and nitric acid
;3, 6-%<.
A considera(ly 5ide section of e,tractants
5as contained esters. =aored esters in
e,tractie *etal- lur$y rise fro* phosphoric
acid and can (e diided to
acidic and neutral esters ;"<. The e,traction
of -irco-
niu* and hafniu* salts fro* 01'
3
, 02l,
02l'
3
and 0
2
+'
3
into neutral
or$anophosphorus co*pounds (1'P2)
proceeds throu$h a solation *echanis* ;9<.
As a neutral ester, tri(utyl phosphate
(T4P) for*s
>2orrespondin$ author! As$har
sadi$-adeh8 ?-*ail!
sadi$-adeh@yahoo.co*
Tel! (A9%) 2" %%22"093
=a,! (A9%) 2" %%22"093
additional co*pounds 5ith *any *etallic
nitrates, chlorides and thiocyanates.
2o*pared 5ith T4P, co*pounds 5ith *ore
(ase phosphoryl $roup, PB', are (etter
e,tractant than T4P. ?,tracta(ility increase
5ith follo5in$ arran$e*ent ;"0<!
Phosphine C phosphinate C phosphonate C
phosphate
The e,traction *echanis* of 9r and 0f
5ith T4P inoles the hydrated 9r ion
for*in$ a neutral *ole- cule and solate
for*in$ at the a7ueous-or$anic inter- phase
o5in$ to the coordination (ondin$ (et5een
9r and 0f ato*s and the o,y$en of the
phosphoryl o,y- $en. 9irconiu* salts for*
*ore sta(le T4P e,tracta- (le co*ple,es than
do hafniu* salts ;3<. These co*- pounds
the*seles are solu(le in T4P and therefore
can (e efficiently e,tracted ;D<.
/n $eneral, one should 6eep in *ind that
the -ir- coniu* ions e,traction a(ility is
stron$ly dependent on the nature of the initial
co*pound. T4P e,tracts
-irconiu* fro* sulfuric acid solutions only at
hi$h
concentrations of 0
2
+'
3
. The -irconiu*
co*pounds e,traction a(ility aries as!
nitrateC chlorideC sulfate
C (ro*ide
;9<.
/n so*e syste*s for control of $oernin$
che*i- stry of co*ple, for*ation reaction
(et5een *etal and e,tractant, (ecause of
e,tracta(le species for*ation in particular
acidity, total concentration of hydro$en ion
5as 6ept in deter*ined ran$e ;3, "3-"#<.
Accordin$ to :ailen 5or6 ;3<, (et5een
e,istent species of 9r-e,tracta(le and
ine,tracta(le in a7ueous solution, 9r
A3
and
9r('0)
A3
species are e,tracta(le. Also, in the
case of 9r ion e,traction fro* nitric acid
+adi$-adeh et al.
Journal of Theoretical and Applied Physics, 3-3 (2009)
*edia, other 9r species such as 09r(1'
3
)
#
and 0
2
9r(1'
3
)
6
hae (een su$$ested to (e
e,tracta(le into T4P. /n this case, the 9r
A3
ions predo*inate in solu- tions containin$
*ore than 3: 01'
3
. The chan$e in the
*echanis* of -irconiu* e,traction into T4P
in
the hi$h acid concentration ran$e has (een
confir*ed
;3, D,
9<.
The partition of -irconiu* (/E) (et5een
hydroch- loric acid solutions and solutions of
tri-n-(utyl phos- phate (T4P) and of di-(2-
ethylhe,yl)-phosphoric acid
()?0PA) in 6erosene has (een
inesti$ated under
different conditions. The effect of or$anic
solent in the e,traction (y )?0PA has also
(een e,a*ined ;#<.
=ro* *i,tures of inor$anic acids, 1'P2
e,tracts -irconiu* and hafniu* 5ith
separation factor consi-
dera(ly e,ceedin$ the correspondin$ alue
for e,trac-
tion fro* solution of indiidual acids. /t
has (een found that nitrate-fluoride, nitrate-
chloride and nitrate- per chlorate co*ple,
hae an enhanced e,tracta(ility. A still hi$her
separation is o(tained 5hen usin$ *i,- ture
of acids, especially those of nitric-
hydrochloric acids. A sharp enhance*ent of
-irconiu* e,tracta(ili- ty fro* hydrochloric
acid 5ith addition of sulfuric acid has (een
caused (y the dehydration action of sul- furic
acid ;9<.
Fan$ et al. ;"6< studied the e,traction of
-irco- niu* fro* solutions of perchloric and
nitric acid 5ith tri-n-(utyl phosphate (T4P)
in 6erosene. Accordin$ to their results, 5hen
the initial 02l'
3
concentration 5as
less than 6 *ol&d*
3
, there 5as hardly any
for5ard
transfer of 9r(/E) into the or$anic phase, (ut
5hen the concentration 5ent up to % *ol&d*
3
,
the percent e,- traction increased sharply
until *ore than 90G e,trac- tion 5as reached.
The effect of te*perature on e,traction
reactions 5ith T4P can (e different under
arious conditions $oerned on e,traction
process. +o that, in e,traction of *oly(denu*
fro* sulfuric acid and rhodiu* fro*
hydrochloric acid *edias e,other*ic and
endother*ic reactions happen respectiely ;2,
"#<.
As *entioned, the inesti$ation on
*i,tures of neutral phosphorous esters and
diluents can lead to discoer a *utual
interaction. This inesti$ations indi- cated
that *i,in$ of T4P and heptan, nonan and
decan is acco*panied (y heat adsorption
5hereas its *i,in$ 5ith chlorofor* or car(on
tetrachloride is an e,o- ther*ic reaction. /n
the first case, heat adsorption is due to
deco*position of T4P di**ers in
hydrocar(on diluents 5hereas in the second
case e,other*ic reac- tion is due to T4P
co*(ination 5ith chlorinated hy- drocar(ons
for the purpose of 22l
3
.2T4P and 202l
3
.T4P
for*ation. These (onds decrease lar$ely
effectie concentration of T4P in or$anic
phase and e,traction concentration of diluted
T4P 5ith chloro- for* and car(on
tetrachloride. Also, accordin$ to our
e,peri*ents, in e,traction syste*s containin$
T4P&22l
3
or 202l
3
, separation of a7ueous
and or$an- ic phase needs fe5 *inutes.
Therefore, 5e choose 6erosene as an
unchlorinated hydrocar(on diluent to
3
+adi$-adeh et al.
Journal of Theoretical and Applied Physics, 3-3 (2009)
+olent e,traction of -irconiu* H
Journal of Theoretical and Applied Physics, 3-3 (2009)
preent the decrease of T4P e,traction a(ility
and accelerate the separation of phases in this
syste* ;"<.
Ierosene as a refinin$ product of oil is
for*ed (y co*ple, of unsaturated cyclic,
aro*atic al6yl, and
chain hydrocar(ons ;"<. The aro*atic
co*pounds
preent considera(ly the e,traction of heay
*etals
;"2<
.
/n another research, s*all-an$le neutron
scatter- in$ (+A1+) data for the tri-n-(utyl
phosphate (T4P)- n-octane, 01'(3)-
9r(1'(3))(3) solent e,traction
syste*, o(tained under a ariety of
e,peri*ental con-
ditions, hae (een interpreted usin$ the
4a,ter *odel for hard spheres 5ith surface
adhesion ;%<.
Ta$uchiJs *ethod ;"D< 5as used to
deter*ine the opti*u* conditions for
separation of -irconiu* fro*
hafniu* (y solent e,traction. The
e,peri*ental con-
ditions 5ere studied for three different acids
and T4P, )2?0PA or 2yane, 2D2 as
e,tractant. The opti*u* e,traction of
-irconiu* and opti*u* -irco- niu*&hafniu*
separation 5as also achieed usin$ this
co*(ination ;6<.
/n this 5or6, the e,traction of -irconiu*
fro* so- lution containin$ nitric-hydrochloric
acids usin$ T4P in treated 6erosene as diluent
has (een inesti$ated.
4ecause there are not sufficient reports on the
e,trac-
tion of -irconiu* fro* solution containin$
nitric- hydrochloric acids 5ith T4P.
The follo5in$ para*eters hae (een
aried! *i,- in$ ti*e, the e,tractant, nitric
and hydrochloric acids and -irconiu*
concentrations, acidification of or$anic
phase, the or$anic&a7ueous phase ratio and
te*pera-
ture
.
".
*x+erimental
2.". Rea$ents and
solutions
The 6erosene, used as diluent in this
study, 5as a co**ercial product. The or$anic
phase 5as prepared (y dilutin$ T4P in
6erosene. 1itric acid (6#G) and hydrochloric
acid (3 #G) 5as proided fro* :erc6, 9r2l
3
and 0f2l
3
5ere of analytical rea$ents $rade.
)ou(ly distilled 5ater 5as used for preparin$
all the solutions.
As a source of 9r(/E) and 0f(/E),
9r(0f)'2l
2
5as prepared (y dissolin$
9r(0f)'2l
3
in deioni-ed 5ater. 9irconiu*
tetrachloride in contact 5ith 5ater hydrolyses
ery readily and for*s o,ychloride ;"3<
9r2l
3
A0
2
'K 9r'2l
2
A202l
(") Therefore 5ith solation of -irconiu*
tetrachlo-
ride in 5ater, e,istence of hydrochloric acid is
certain and its a*ount is related 5ith
concentration of -irco- niu* n solution.
2.2. +olent e,traction
procedure
?,traction e,peri*ents 5ere carried out
usin$ *echanically a$itated techni7ue. The
*i,ture 5as
3
3
a$itated (y an electro*otor 5ith a constant
stirrin$ rate. After *i,in$ for # *in, the
or$anic phase 5as separated fro* the
a7ueous phase.
The -irconiu* ion concentrations 5ere
deter- *ined in a7ueous phase (y titration
5ith ?)TA and e*ployin$ ,ylenol oran$e as
a rea$ent. The *etal ion concentrations in the
or$anic phase 5ere calculated fro* the
difference (et5een the *etal ion concentra-
tions in the a7ueous phase (efore and after
e,traction. The results are $enerally
e,pressed as percenta$e *et- al e,traction.
3. ,esults and
discussion
/n this section the e,peri*ents perfor*ed
on four different cases and the effect of
i*portant para*eters are presented.
a. The effect of or$anic phase
para*eters such as percenta$e of
e,tractant on e,traction of 9r.
(. The effect of *ain a7ueous phase
para*eters such as concentration of
-irconiu*, nitric and hydrochloric
acids, and e7uili(riu* hydro$en on
e,traction process.
c. The acidity of or$anic phase and its
effect on -irconiu* e,traction.
d. The effect of $oernin$ condition on
*i,in$ *ediu* inolin$
te*perature, or$an-
ic&a7ueou phase ratio on e,traction
process.
3.". ?,traction reaction
studies
The e7uili(riu* e7uation of *etal ions
e,traction fro* a7ueous solutions 5ith
12P2 as an e,tractant can (e descri(ed in
the follo5in$ 5ay
s+
(or$.)
A*:
(a7.)
AaA
(a7.)
B;A
a
.:
*
.+
s
<
or$.
(2)
5here + is the e,tractant, : is the anion or
cation ion and A is any counter ion or other
species that *ay (e present in the a7ueous
phase.
3.2. ?ffect of arious para*eters on the
e,traction of -irconiu* fro* acidic solutions
The effect of contact ti*e, concentrations
of e,- tractants, nitric and hydrochloric acids,
'r$an- ic&A7ueous ('&A) phase ratio,
e7uili(riu* hydro$en ion and -irconiu*
concentrations and acidification of or$anic
phase on the e,traction of -irconiu* has (een
inesti$ated and the results are reported in
=i$s."-D.
3.2.". ?ffect of contact
ti*e
The e,traction e,peri*ents 5ere carried out
for con- tact ti*es ran$in$ fro* 2 to "# *in.
The operatin$ conditions of e,traction 5ere!
;02l<
a7.
B ;01'3<
a7.
B
3.6 :, ;9r
A3
< B 62.#$&lit, ;01'
3
<
or$.
B".D :, ;T4P< B
2.2 : at roo*
te*perature.
The *etal e,traction percenta$e increases
5ith contact ti*e. The e,traction e7uili(riu*
5as esta(- lished after 2-3 *in (D6.#G for
'&AB" and 93.%G for '&AB2.l#). 0o5eer,
in all e,traction e,peri*ents a contact ti*e of
# *in (D%.#G for '&AB" and 93.#G for
'&AB2."#) 5as chosen for ensurin$ that the
e7ui- li(riu* 5as reached.
Accordin$ to these data, e,traction of
-irconiu* (y T4P usin$ *i,er settlers
doesnLt need the lon$ resident ti*e in *i,ers
or $reat stirrin$ rate. Also, in
the case of hafniu* e,traction, si*ilar to 9r,
the e,-
traction needed no lon$ ti*e. Therefore,
*i,in$ ti*e can not (e a separation
controllin$ factor. 4ut *i,in$ ti*e study is
necessary for the calculation of e,tractor
di*ensions.
+o*e ti*es for safety of suita(le
e,traction in each sta$e, $reater stirrin$
rate 5as selected. 'f course, this idea can
(e ri$ht, (ut it has so*e pro(-
le*s. /ncrease of stirrin$ rate can cause the
for*ation
of steady e*ulsion in the syste*. /n this case,
fine droplets of a7ueous and or$anic phases
*i$rate into other phase. This causes t5o
pro(le*s8 "-ariation of '&A ratio8 2- due to
different solu(ilities of 6erosene and T4P in
5ater and 5ater in the*, in lon$ ti*es, it can
(e o(sered that the percenta$e of T4P aries
in solent. Also, so*e ti*es part of enriched
phase of hafniu* (output of a7ueous phase)
fro* final sta$es of *i,er settlers Mas
suspended dropletsM *ay *i$rate into
for5ard sta$es or carried (y or$anic phase out
of e,traction syste*. Thus, the decrease of
stirrin$ rate in e,traction state lo5ers the
a*ount of hafniu* in a7ueous production
containin$ -irconiu* ions, after scru((in$
and strippin$ sta$es, fro* "%0 pp* to 0.2
pp*.
3.2.2. ?ffect of concentration of
e,tractants
/n the e,traction process, the increase of
e,trac- tant concentration up to a certain point
increases the distri(ution coefficient of
-irconiu*. /ncrease of e,- tractant after this
leel (threshold point) has no effect on
e,traction percenta$e. 'f course, the situation
of this threshold point aries 5ith different
para*eters such as te*perature, a7ueous
phase acidity, type of diluents and *etal ion
concentration in a7ueous phase.
/n this section, The e,tractant
concentration in solent 5as aried and the
effect on the e,traction ratio of -irconiu*
fro* solution containin$ ;02l<
a7.
B3
:, ;01'3<
a7.
B3 :, ;9r
A3
<B%0$&lit and '&AB" 5as
studied at
"6N"O2.
The plot of ?G s. T4PG is sho5n in
=i$. " and indicates the increase of e,traction
percenta$e fro* 0
to 33.%G (y enhancin$ the e,tractant
concentration
fro* 0 to 60G, durin$ the e,traction process
of -irco- niu*. 4eyond the declared
e,tractant concentration of
60G, the a*ount of e,tracted 9r decreases to
30.#G. Therefore the solent concentration of
60G T4P is chosen for the (est e,traction of
-irconiu*.
Accordin$ to these data, the lo$ ;T4P<
ersus lo$ )
9r
plot - ;T4P< B 0."%-2.2 : - is
strai$ht lines. The alue of the slope is 0.6
and indicates one piece of T4P e,ists in
e,tracta(le co*ple,.
-ig. 1. TBP concentration effect on the
extraction of zir- conium. )n this figure, the
extractant concentration in solvent (as
varied and the effect on the extraction
ratio of zirconium from solution containing
.#!l/a0. 1 3 2, .#34
3
/a0. 1 3 2, .5r
67
/ 1
89g:lit and 4:A 1 1 (as stu- died at 1; <
1=!.
3.2.3. ?ffect of nitric and hydrochloric acids
and hy- dro$en concentrations
Accordin$ to the study on the effect of a
5ide ran$e of a7ueous phase acidities on
-irconiu* e,trac- tion, little a*ounts of
-irconiu* 5ere dissoled in 5ater. /t depends
on the relation (et5een -irconiu*
concentration and hydrochloric acid *olarity
in feed solution. Therefore, 5ith dissolin$
$reat a*ounts of -irconiu*, lo5er *olarity
of 02l is not pro(a(le.
The effect of nitric and hydrochloric acid
concen- trations ("-3 :) on the e,traction of
"0 $&lit 9r(/E) has (een studied usin$ a
solent syste* consistin$ of
60G ol. T4P in 6erosene. The e,traction of
9r(/E)
5as found to increase 5ith the increase in
acid con- centrations. The results are
presented in =i$s. 2 and 3.
Accordin$ to these data, in the cases that
the total hydro$en ion concentration -in
a7ueous phase- is less
than # :, the sensi(le e,traction 5onLt (e
o(sered.
This e,traction (ehaior is related to
so*e para- *eters of syste* such as 6ind of
diluents and e,is- tence of saltin$ out a$ents.
+o that, in the e,traction syste* containin$
T4P&(utyl ether as solent and a7ueous phase
containin$ nitric-hydrochloric acid and 2a2l
2
,
for e,traction of 30-#0 $ 9r&lit fro* feed
solu- tion containin$ total hydro$en ion
concentration e7ual
3 :, )
9r
a(out "-".# 5as o(tained
;3<.
Accordin$ to =i$s. 2 and 3, in ;0
A
<
tot. in a7.
P D :,
the e,traction procedure aries and the slope of )
9r
cures aries sharply. The sudden ariation
of the
e,traction procedure sho5s the chan$e of
e,traction *echanis* (ecause of the chan$e in
e,tracta(le spe- cies.
-ig. ". *ffect of nitric and hydrochloric
acid concentra- tions on the extraction
of zirconium& .5r
76
/ 1 19 g:lit, .TBP/ 1
"." 2, 4:A1 1, and tem+. 1 "9 < 1=!.
-ig. 3. *ffect of .#
6
/ on the
extraction of zirconium& .5r
76
/ 1 19
g:lit, .TBP/ 1 "." 2, 4:A1 1, and tem+.
1 "9 <
1
=
!
.
/n an industrial desi$n, 5e should pay
attention to this point that input feed to
e,traction unit for hain$ an econo*ic
e,planation, a solution 5ith $reat con-
centration of -irconiu*, a(out %0-90 $&lit
*ust (e utili-ed. /n this case, due to
relation (et5een 02l and 9r ion
concentrations in feed solution, ?7. ",
under the condition, %0- 90 $ 9r&lit,
hydrochloric acid concentra- tion is
appro,i*ately *ore than 3 :. =or access
to re7uired *ini*u* ;0
A
<
tot.
to accepta(le
9r e,traction -
# :- nitric acid concentration *ust (e
*ore than 2 :. Also, 5ith the increase of
acidity up to ;0
A
<
tot
.B D : - in feed sol. -
separation factor falls sharply.
Accordin$ to our e,peri*ents *ain
controllin$ a$ent of e,traction and
separation of -irconiu* and hafniu*
process is nitric and hydrochloric acid con-
centrations.
The 5ei$ht of effect of each of the t5o
affectin$ ele- *ents on the e,traction, the
concentration of 01'
3
and 02l in a7ueous
solution is inesti$ated 5ith the Ta$uchi
statistical *ethod ;"D<. To e,a*ine t5o pa-
ra*eters 5ith 3 leels, Ta$uchi proposes Q
9
array con- tainin$ 9 tests. =or replacin$ of
results, 5e used the data e*ployed in =i$. 2.
:ain factors and (ased conditions for this
process are sho5n in ta(le".
Ta%le 1. 2ain factors and their a++ointed
levels. .5r
76
/ 1
19 g:lit, .TBP/ 1 "." 2, 4:A 1 1, and tem+.
1 "9 < 1 =!.
2ain factors uni
t
>evel
1
>evel
"
>evel
3 ;01'3< *ol&
lit
2 3 3
;02l< *ol&
lit
2 3 3
3.2.3. The effect of '&A phase ratio
The operatin$ conditions used 5ere ;02l<
a7.
B 3 :,
;01'
3
<
a7.
B 3 :, ;9r
A3
< B %0 $&lit, ;T4P< B 2.2
:, ;0
A
<
or$.
B ".9# : and *i,in$ ti*eB # *in
at"6 N " O2. The '&A phase ratio 5as aried
(et5een "&2 and 3&". The results are sho5n in
=i$. 3. The e,tracted *etal, percenta$e
increased 5ith increasin$ the '&A phase ratio.
The ariation of the phase ratio fro* "&2 to
3&" lead to an increase in the percenta$e of
e,tracted *etal fro* 3#.#3 to 9#.2G. 4eyond
ratio 3&", the phase ratio had little effect on the
*etal e,traction. Therefore, this point 5as
e,plained as a threshold point.
-ig. 7. )nfluence of the 4:A +hase ratio on
5r extraction& .#!>/a0. 1 .#34
3
/a0. 1 3 2,
.5r
76
/ 1 89 g:lit, .TBP/ 1
"." 2, .#34
3
/org. 1 1.?@ 2, 4:A 1 1,
mixing time 1 @ min and tem+.1 1; < 1 =!.
The 4:A +hase ratio (as va- ried %et(een
1:" and 7:1.
2ertainly, the threshold point can ary
under dif- ferent conditions (such as different
concentrations of nitric and hydrochloric
acids and -irconiu* in a7ueous phase,
te*perature, e,tractant percenta$e and
diluents). =or e,a*ple, in contactin$ of
solution con- tainin$ ;02l<
a7.
B 3 :, ;01'3<
a7.
B
3 : and ;9r
A3
< B "0 $&lit 5ith or$anic phase
containin$ 60G T4P in 6ero- sene, for '&A
ratio B "&", up to 9%G -irconiu* content 5as
e,tracted. /n this case, increase of '&A ratio is
not effectie and suita(le.
3.2.#. ?ffect of -irconiu*
concentration
The operatin$ conditions used 5ere
;02l<
a7.
B 3
:, ;01'
3
<
a7.
B 3 :, ;T4P< B 2.2 :, ;0
A
<
or$.
B ".9# :,
and *i,in$ ti*e B # *in at "6 N " O2 in this
case in-
crease of 9r concentration fro* # to 90 $r&lit
causes a decrease in )
9r
fro* "".% to ".
Therefore, relation of )
9r
and 9r concentration
5as follo5ed (y ?7. 3!
)
9r
B 3R"0
-D
R;9r
A3
<
3
a7.
-"0
-3
R;9r
A3
<
3
a7.
A 0.0"33;9r
A3
<
2
a7.
-
0.6903;9r
A3
<
a7.
A"#.003 (3)
=i$. # sho5s :c2a(e-Thiele plot ;"< for
9r(/E) e,traction. /n ;02l<
a7.
B 3 :, initial
concentration of 9r in a7ueous solution can not
(e *ore than "00 $r&lit. Therefore, this cure
contained li*ited nu*(er of e7uili(riu*
points.
2hoosin$ a special operatin$ line for
e,traction process depends on so*e para*eters
such as T4P content of or$anic phase and acid
concentration in a7ueous phase. These
para*eters effect on solents loadin$ capacity
and e,traction a(ility of 9r ions. +o that for
hain$ a suita(le e,traction fro* solution con-
tainin$ 60 $ 9r&lit under *entioned operatin$
condi- tions, 5e can not e*ploy '&A B "
condition. =or in this case e,tractant loadin$
capacity is fe5er than 60 $ 9r&lit. +o under this
conditions *otion on e7uili(riu* cure is not
possi(le. Shereas if 5e choose '&A B 2, een
suita(le e,traction fro* solution containin$ %0
$ 9r&lit is possi(le.
-ig. @. 2c!a%eAThiele +lot for 5r B)CD
extraction.
3.2.6. ?ffect of
te*perature
The effect of te*perature on the e,traction
of -ir- coniu* 5as studied (y chan$in$
te*perature (et5een
"# O2 and 63 O2 at a constant T4P
concentration. /t can (e seen fro* =i$. 6 that
)
9r
increases 5ith te*- perature.
-ig. ;. *ffect of the tem+erature on 5r
extraction& .#!>/a0. 1 .#343/a0. 1 3 2,
.5r 7 6 / 1 89 g:lit, .TBP/ 1 "." 2,
.#343/org. 1 1.?@ 2, 4:A 1 1, and mix- ing
time 1 @ min.
/n =i$. 6, the slope of line is -2%0.9.
Therefore, the apparent standard enthalpy of
the e,traction reac- tion is #.3% 6J&$.*ol. +o
the e,traction of -irconiu* fro* nitric-
hydrochloric a7ueous *edia 5ith T4P is an
endother*ic reaction. 4ut ariation of
te*perature has no $reat effect on e,traction
of -irconiu* (y T4P8 so that, 5ith increase
of te*perature fro* "# O2 to 63
O2 percenta$e of e,traction 5as 2D.DG and
32G, re- spectiely.
Shen loadin$ capacity of e,tractant
approach to saturation point, the e,tractant
does not hae sensi(le
a(ility to e,traction of -irconiu* ions. /n this
case, *i,in$ of this e,tractant 5ith a7ueous
phase contain-
in$ $reat concentration of -irconiu* (for
e,a*ple solution containin$ ;0
A
<
tot.
B 6 : and
"00 $ 9r&lit).
Sith increase of te*perature up to "0 O2
durin$
e,peri*ents, crystalli-ation of a7ueous phase
*ay occur suddenly. 4ecause in this
conditions, part of acid and 5ater e,tract
into or$anic solent and e,trac- tion of
-irconiu* does not happen. Therefore
concen- tration of -irconiu* increases in
a7ueous phase and su(se7uently sudden
crystalli-ation due to increase of -irconiu*
concentration and lac6 of te*perature hap-
pens.
3.2.D. ?ffect of or$anic phase
acidity
The effect of nitric acid concentration in
or$anic phase 5as inesti$ated 5ith contact
of the acidic or- $anic phase 5ith a7ueous
phase containin$ -irconiu* ion.
)ecrease of (oth a7ueous and or$anic
phase o- lu*e ariations is one of the
reasons for acidified or- $anic phase in
industrial e,traction processes of -irco- niu*,
usin$ T4P.
:ainly t5o features of acid e,traction (y
phos- phorus esters such as T4P hae
receied continuous attention. These are the
capacity of esters to e,tract, or
to dissole, acids 5ell oer an acid-to-ester
ratio of
unity, and the hydration of the acid in the
or$anic so- lution. ?,traction of 01'
3
is
dependent on (oth a7ueous phase acid and
T4P concentrations ;3<.
Ta%le ". *ffect of organic +hase acidity in
extraction of zirconium and volume
difference of a0ueous +hase& .#34
3
/a0. 1
.#!l/a0. 1 3 2 and .5r
76
/ 1 89 g:lit and 4:A
1 1 at 1; < 1 O!.
.#34
3
/
org.
,
-inal vol.
4f a0.
E*xtract
ion of
-inal
acidity of
0.
0
"
%.
3
3.
3
.
".
6
"
9.
#
6.
#
.
".
9
"
9.
#
%.
#
.
Accordin$ to the o(tained data, e,traction reac- tion
rate of nitric acid (y T4P is fast. +o that, in *i,- in$ ti*e
less than 0.# *inutes, the e,traction of acid is co*pleted.
Therefore, in this case, acid e,traction did not need the
lon$ residence ti*e or $reat stirrin$ rate in *i,ers.
Also, (ased on the o(tained e7uili(riu* cure
of nitric acid e,traction (y 60G T4P&6erosene, *ost
concentrations e,tracted (y solent 5ere 2 :
appro,- i*ately and to find a situation that consist
*ore acid concentration in the or$anic phase is not
possi(le (=i$.
D). 'f course, this saturated point is related to
te*per- ature, percenta$e of e,tractant and diluent
type in the syste*.
4ased on these e,peri*ents, usin$ unacidified
or- $anic phase for e,traction of -irconiu* under the
con- dition *entioned a(oe, there is "0G deduction
in a7ueous phase olu*e, (ut (y usin$ acidified
or$anic phase, olu*e deduction reduces to 3G
(Ta(le 2). Therefore, $enerally in all of the
e,traction processes the '&A ratio 5as al*ost
constant.
-ig. F. *0uili%rium curve of #34
3
extraction %y
TBP Ta%le 3. *xtraction of zirconium from
a0. Phase in some
stages %y unacidified solvent. .#34
3
/a0. 1 .#!l/a0. 1 3
2 and .5r
76
/ 1 89 g:lit and 4:A 1 1
at 1; < 1O!
St
a
g
-ir
st
conc.
-in
al
conc.
-irst
vol. of
a0.
-inal
vol. of
a0.
" %0.0 60.2 #
0
3#.#
2 60.2 6".3 3
0
3D.3
3 6".3 63.6 3
0
2%.2
Accordin$ to the e,peri*ental data, (y usin$ un-
acidified T4P for a fe5 sta$e e,tractions fro* the
solution 5ith total acidity e7ual 6 :, after first sta$e of
e,traction, a7ueous phase acidity decreases to 3.2
: (Ta(le 3). This is (ecause in the a7ueous total
acidity under # :, there is no e,traction fro* a7ueous
solution8 therefore, it ter*inates the -irconiu* e,trac-
tion after the first sta$e.
0o5eer in each sta$e, e,traction of acid and 5a-
ter happens. Therefore, olu*e of a7ueous phase de-
creases in each sta$e. +o, the a7ueous phase acidity in
each sta$e is reduced, e,traction does not happen and
the concentration of -irconiu* in a7ueous phase de-
creases due to its olu*e reduction and *ass constan-
cy of -irconiu* in a7ueous phase.
Therefore, in the industrial processes, acidifica-
tion of or$anic phases due to control of '&A ratio and
resort of suita(le e,traction of -irconiu* is necessary.
7. !onclusions
Qi7uid-li7uid e,traction studies of 9r (/E) fro*
solutions containin$ nitric-hydrochloric acids (y
T4P&6erosene sho5ed that acid concentrations hae the
*ost effect on the 9r e,traction. /n this case, there is no
e,tracta(le -irconiu* and hafniu* species under the
condition ;0
A
<
tot.
B # : in a7ueous solution. Also,
after ;0
A
< B D : the *echanis* of e,traction
reaction
aries and increases sharply. Also, or$anic phase
aci- dification is necessary for industrial
processes. Ac- cordin$ to our data te*perature
has poor effect on the aforesaid e,traction.
,eference
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:ara$heh, 0ydro*etallur$y,
?9, ""# (200%).
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Tucson Ari-ona ("99%).
;"3< R. 2alet6a, 2he*ic6e Qist, @8, 339 ("963).
;"3< 4. R. Reddy, J. R. Iu*ar,
0ydro*etallur$y, F7, "D3 (200#).
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