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FluidPhase Equilibria, 53 ( 1989) 235-242

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

A NEW NODEL FOR METAL


YI-GUI

LI, JI-DING

Department
Beijing,

SOLVENT EXTRACTION

LI, JIU-FANG

of Chemical

LU and

Engineering,

235

SYSTEM

TENG TENG

Tsinghua

University,

China

ABSTRACT
In this paper, the LLE experimental
xyl) phosphoric
were measured
to predict
organic

acid

data for di(2-ethyl

(D2EHPA)-nC7H16-Cos04-CuS04-H2S04

and listed.

the component

A new thermodynamic
activity

model was used

coefficients

in quaternary

phase, only by using three corresponding

systems.

The real thermodynamic

chemical

reactions

involved

equilibrium

he-

system

ternary

constants

VLE

for two

system were de-

in the extraction

termined.
INTRODUCTION
The metal solvent
in nuclear

industry

and automatic

extraction

process has been widely

and hyorometallurgy.

control need component

The process

distribution

used

design

an0 activity

Coefficient data anu equilibrium constants for the LLE system.


In recent years, the authors (1982,
1986,
1987
and 1988)
usea
the Scatchard-Hildebrand
se and the Pitzer
solvent

equation

equation

extraction

systems.

tion is that the terminal


systems

distribution
proposed

constants

function

tion of the component


The component

0378-3812/89/$03.50

from binary

in multicomponent

as a damping
activity

activity
equation

oscillation

thermodynamic

model

coefficients

coefficients

from corresponding

ty coefficient

Aij obtained

systems.

Li et al. (1988) treated the molecular

a new molecular

be predicted

the organic pha-

to aqueous phase for various metal


The main problem of using SH equa-

cannot be kept constants

cently Ji-ding

to correlate

sine curve

in organic

for ternary

0 1989 Elsevier Science Publishers B.V.

and

for the calculaSOlUtiOn.

VLE systems

binary VLE systems.

is as follows:

Re-

radial

can

Our activis

236
lnfj=FCiaij+f(uiCj/Cj)Rij+

ln(#j/Xj)+

1 -1sj/Xj - Cg(Ajj+Bjjll)

In thi; paper, we use the above equation


-CuSO4-H2SO4
separation

extraction

system, which
in hydrometallurgy.

to D2EHPA-nC7H16-Cos04

is important

in Co and Cu

EXPERIMENTAL
Reagents
--D2EHPB

(di(2-ethyl

CH2)2P04H))

cupric salt method.


Cu(~R2)~.2H20
the dimer

hexyl)

phosphoric

acid

(CH~(CH~)TCH(L~H~)

used as extractant

was C.P. reagent and purified by


organic complexes Co(HR2)2_2H20 and

Metal

were synthesized

of D2EHPA.

and purified.

Normal heptane

Here H2R2 denotes

(nC7H16) used as a diluent

was A.R. grade.


Aooaratus

and
Procedure
-----All the LL~ experiments

carried out in centrifugal tubes (25 ml), fitted with ground stoppers, in a thermostatic
chamber

at 25+0.2'C

equilibrium,

were

and shaken for 40 minutes.

two liquia

phases were separated

After reaching
by centrifugal.

The densities for both phases were measured by densimeter. The


organic phase was transfered to a sample vial to make VLE measurement

by SP2305 gas chromatograph

Analytical

Instrument

space sampler
schematic

by the Beijing

r'actory) combined with automatic

(made by American

diagram

(produced

Hewlett-Packard

of the experimental

head-

Company).

equipment

is shown in Fig

1 . The equilibrium concentrations of Co and LU in both liquid


phase, of H2SO4 and pn in the aqueous phase were measured, respectively.
nqueous

solutions

CuSO4 and organic

with different

solutions

tial concentrations

concentrations

of D~EHPA-C~HI~

of D2EHPA

(0.4, 0.5, 0.589,

O.SM) were added to the tubes at a volume


series

of Co+304 and

with different
0.68,

ini-

0.725

and

ratio of 1:l. Every

of experiments

with the same initial concentration of


D2EHPA (C20) had 7-8 samples with different concentrations of
coso4 and CuSO4 in the aqueous phase. There were 7 series of
experiments

including

53

equilibrium

data points altogether.

The LLE experimental data thus measured are listed in Table 1.


Besides this, we added 18 equilibrium data points with different lower

initial

concentration

and with lower metal


der to complete

of D2EHPx

concentration

in organic

in aqueous

the integra!.s more accurately.

solution

Solution
in

Or-

237

Fig.

equipment
1. Schematic diacrnm of experimental
1. sample vial, 2. stirrer; 3. therniostatted water bath,
4. magnetic stirrer, 5. temperature
controller, 6. insulatinc material, 7. vacuum system, 8. six-port flas sampline valve, 9. carrier gas (N2) cylinder, 10. regulator,
11. SP2305 <as chromatograph,
12. A/ll signal converter,
13. integrator, HP MX21, 14. signal recorder, T: thermometer,
valves.

DATA TRXATM>SNT
The extraction
-CuSO4-H2S04

reactions

involved

in the D~RHPA-C~H~~-COSO~

system are as follows:

Co2+ + 2H2R2 + 2X20 = 2H+ + CO(HR~)~.~H~~


Cu2+ + 2H2R2 + 2H20 = 2H+ + CU(HR~)~.~H~O

The thermodynamic
may be written

equilibrium

constants

of the above reactions

as follows:

Kco = m~a,,,x3f~/(mco~coa~x~f~) = K3f;/f;'

(2)

Kcu = m:a:xqfz/(rn curcua',xify) = Kqf!/fy

(3)

where K-j = m~a,'x3/(mco~coa~x~) and K4 = rn?,~~x,/(m,ur,,a~x~).


For aqueous phase, we consider all ionic species (H+, HSOi,SOi-,
Cc?and C;*) and the ionic equilibrium:
tzer equations
to calculate

for mixed

electrolyte

the individual

HYO~ = H*+ SOT. The Pi-

solution

ionic activity

(1979) are used

coefficient

for iOn

i (Vi) in aqueous
in electrolyte

solution and also the activity of water (a,)


solution. The calculated results are listed in

Table 2.
If we neglect the free water in organic phase and suppose
all the water dissolved in organic phase is combined with metallic complexes as hydrates, the equilibrium organic phase

238

TBBLS 1
The LLE experimental data for D~EE~PA-C~I:~~-COSO~-CUSO~-H~SO~
system at 25C
C20(K)
no mco
mcu
mH (m/kg:)
x1
x2
x3
0.4038

0.4988

0.5082

0.5890

0.6816

0.7250

1
2
3
4
5
6
7
8
9
IO
11
12
13
14
15

0.0928
0.0835
o.c1791
0.0778
u.0697
0.0619
0.0514
0.236
0.212
0.183
0.156
0.123
".0946
0.0602

0.229

u-0176
0:Olii
o.uo70
0.0044
0."026
0.0~14
0.0007
0.0110
0.0055
0.0029
0.0017
0.0012
o.oou7
0.0003
0.0313

1;
1;

0.184
0.209
0.133
0.162

0.0224
0.0163
ply

20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
27
38

0.107
0.0790
0.0528
OIljO
0.106
0.0845
0.0593
0.0375
0.0206
0.0096

0.335
;a;

0:0058
0,OOjY
0.0026
"io304
0.0187
0.0119
0.0073
0.0043
0.0023
0.0012
u.0084
0.0053
0.0033
0.0024
0.0013
0.0008
0.0005
oIoooj
0.0454
ym;

0:239

u:Ol6Y

0.198
0.163
0.126
0.0914

0.0126
0.0093
U.OO58
0.0039

0.159
0.133
0.105
0.0780
0.0527
u.0319
o.OiSl

k?%;
0:0139
0.0089
0.0053
0.0034
o.OOi9

0.0102

u.0010

0.142
0.130
0.127
0.124
0.116
0.0955
0.0764
0.320
0.296
0.265
0.237
0.208
0.153
0.121
"IO984

zz
41
t;
44

0.7988

----

0.0856
OIO762
0.0539
0.~384
0.0240
0.0125
0.0066

0 185
47 0:178
:z
48 0.172
49 0.164
50 0.156
51 0.144
52 0.120
LG_~.O945

x4

0.9298
0.934~
0.9376
0.9405
0.9445
0.9480
0.9509
0.9050
0.3097
0.9152
0.9205
U.9272
0.3324
U.9392
0.9048
0.9082
0.9128
0.9167
0.9221
0.9270
0.9322
0.3372
0.8821
0.8884
u.8928
0.8985
o.VO41
0.9113
0.9172
0.8511
0.8557
0.8617
0.3671
0.8731

0.0658
0.0570
0.0496
0.0435
0.0352
0.02&O
0.0219
0.0923
0.0827
0.0713
0.0606
0.0470
u.0360
0.0218
0.0900
0.0827
0.0730
0.0647
0.0533
0.0431
0.0321
0.0216
0.1126
0.0993
0.0897
0.0777
0.0655
0.0502
0.0374
0.1439
0.1339
0.1207
0.1090
0.0960

0.8840
0.5908
0.3962
0.8375
0.8433
0.8499
0.8565
u.8648
U.8721

0.0721 0.0439
0.0574 0.0519
0.0455 0.0583
0.0070
0.1555
0.0140
0.1427
0.0219
0.1282
u.0298
0.1137
0.0398
0.0954
0.0486
0.0793

0.8800
0.8876
0.8147
0.8213
0.8284
u.8357
0.8429
~,8501
0.8585

0.0619
0.0451
0.17i2
0.1564
0.1404
0.1241
0.1078
0.0917
0.0728

0.0009
0.0026
0.0034
o.oc37
0.0052
0.0067
0.~087
u.0028
0.0076
0.0135
0.0189
0.0258
0.0317
0.0390

O.OOC7
0.0027
0.0033
0.0041
0.0059
0.0102
0.0144
0.0050
0.0104
0.0176
0.0239
0.031~

0.0025
0.0042
0.~056
0.0076
0.0098
0.0130
0.0194

0.0035
0.0064
0.0094
0.0123
0.0151
0.~173
0.0185

0.0142
0.0185
0:0245
0.0299
0.0357
0.0412
0.0046
0.0097
0.0142
0.0197
0.0245
0.0283
0.0309

0.0581
U-0672
O:Oli7
0.0181
0.0256
0.0326
0.0394
0.0452
0.0492

___0,86._0,9522~,0266__0,051i2_

The relative deviations for the measurement


centration are less than l.G$.

of Co and Cu con-

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-4

F:

240
is

composed

of four components:

(1) nC7H16,

(2) H2R2(D2XHPA.), (

3) CO(I-:R~)~.
2B20 anu (4) Cu(XR,);2HzO.
In this paper, we use
the subscripts 1, 2, 3 and 4 to repretient the component nC7H,6,
H2R2, Co(nR2)2-2B20 and Cu(KR2)2*2H20, respectively. 'I'heactivity coefficient of nC7H,6 was calculated by using our model (
Eq. (1)) as follows:
lnf,=(Cj-CT)B1j+

C2ii12+ C3B13+ C48,4+((C;-C"11)/C'1)",,+(C,C2/C;).

$2+(C1C3/CT )313+(C~C4/~; )R14+ ln(@l/xj )+ 1 -(@j/xl


1 (4)
Here the pure liquid nti7H,6 is taken as reference state. Ci is
the molarity

of component

of pure liquia

component

as the mixed

solution).$i

mole fraction

of liquid

are the interaction

i in solution

and Cf is the molarity

i (at the same temperature


and xi are the volume

component

parameters

anu pressure

fraction

i in solution.

between molecules

and

Aij and Bij


i and j. In Zq.

(4) all the Aij and Bij have been given from the corresponuing
three bi_nary VLE systems
C~H~~-CU(HR~)~*~H~O

(1988) and are listed


C7P16 thus obtained
(see Table

(C7H16-B2R2, C7H,6-~o(11R2)2.21!20, and


which were measured by Ji-ding Li

systems),

in Table 3. The activity

are in agreement

2). The average

than 1.59.
The remaining

relative

three binary

coefficient

with the experimental


deviation

of
data

for f, is less

dLE systems are all composed

0f

non-volatile components. We cannot measure their partial pressure at 25C by gas-chromatograph


directly, anu we do not have
enough

interaction

have t0 predict
non-volatile

parameters

the dctivity

components

ed with the chemical


brium equations.
ting Zq.(2)

for further
coefficient

by use 0f Gibbs-Duhem

equili-

Differentia-

Table
ecules

equation

SO we
combin-

parameters
between
mol3~ Interaction
(Aijand Bij)at 25C

and (3) at cons-

tant pressure

HA

and temperature,

we get:

Co(HW,
.2H,O

CuWR,),
.2&O

-0.1362

-03049

-2.456

dlnK3 + dlnf* - 2dlnfs = 0 (5)


a
alnK4 + dlnf4 - 2dlnf: = 0 (6)
The Gibus-uuhem
this quaternary

equation for
organic phase

is as follows;
x,dlnf,+

calculation.

for the other three

x2dlnf;+

x3dlnf;+

dlnfi = 0
Eere the star (*) denotes

x4
(7)
the

-5.729
H,R,

a4039

241

infinite

dilution

convenience.

was used for solutes

From Eq.(5),(6)

and

as reference

state fop

(7), we can solve the fi, f:

and fi:

J (x7/X)dlnK3+j(x4/X)dlnK4-j(x,,X)dlnf,

lnf:=

(8)
(9)
lnfi= J(2x7/X)dlnK3-j((2x3+x2)/x)dlnK4-J(2x,/X)dlnf,
(10)
where d = x2+ 2x + 2x4. The predicted activity coefficients of
lnf;= -I((x2+2x4)/X)dlnK3+j(2x4/X)dlnK4-J(2x,,X)dlnf,

components

2, 3 2nd 4 thus obtained

The thermodynamic
reactions

tants in the whole


D2EHPA

equilibrium

can be obtained

in Table 2.

for the extraction


They are real cons-

range, no matter what initial

and what degrees

in the organic

are in the aqueous

constants

simultaneously.

concentration

concentrations

dissolved

are listed

of saturation

of metals

phase are, and what ionic strengths

phase

(see Table 4).

TABLB j
The predicted
reactions
of

thermodynamic
Co and Cu by

equilibrium
u~EHPA (at

constants
25C)

B2bPAconc,T~-~T4078OT?~~--~508--OTS8B~jT~816~~-~-;8
extracted
metals
Co,Cu
CO
:
degree
of GOof+ satu.
cu (Z)
7P-3
79.23
o-1:0
I range
o-1 .o
xc0
(lo+
)
5.20
5.25
/
Kcu (10)
1.33
1:
1.44
data
noints
9
12

Our preliminary
mic model

deduced

component

c;o,cu

extraction

co

7:,7t3
o-1.2
5.20

1.33
11

cu

71.93
OU-l .3
5.25
/
13

the component

liquid-liquid

oscillation

activity

equilibrium

co,cu

740187
O-1.4
/
1.44
14

study shows that our molecular


from the damping

used to calculate

for

770,96
o-1.4
5.20

1.33

thermodyna-

equation

coefficient

with chemical

13

can be

for multi-

reaction

sa-

tisfactorily.
ACKI<O:JLEDGEMENT
The authors

appreciate

ch by China Natural
LIST OF SYMBOLs:
A, B interaction
a
activity

the financial

support

parameters

between

molecules

in our new model

concentration

C"

concentration of pure liquid in molarity


initial concentration of D2EHPA in organic
larity

C20
f

of this reoear-

Science Founda'ion.

in molarity

activity coefficient
ference state

solution

in mo-

for solvent with pure liquid as re-

242

activity coefficient
reference state

ionic strength

for solute with infinite

in aqueaus

K CO' Kc, thermodynamic


tions
concentration

inmolality

mole fraction

for organic

individual

volumn
$
Subscripts

ionic activity
fraction

i, j molecule

co

index:

cobaltous

as

solution

equilibrium

m-

dilution

constants

for aqueous

for chemical

solution

reac-

(mol/kgH20)

solution
coefficient

)2.21!20 and 4-

ion

cu

cupric

hydrogen

ion

ex

experimental

ion
value

REFER!WCES
Li, J.D., Y..ti.hi and J.F'. Lu, 1988. Proceedings of International symposium on Thermodynamics in Ghemical dngineering and
Industry, China, 339-346.
Li, Y.G., T. Teng, Z.n. Cheng and L.P. Zhang, 1982. Hydrometallurgy, 8: 273-287.
Li, Y.G., T. 'reng, J.F. LU, G. Chen and J.u. Li, 1986. r'luid
Phase dquilibria, 30; 297-306.
Li, Y.G., J.F.
Lu,
Z.C. Li, T.L. baa, J.u. Li and T. Teng, 1987.
aeparation Processes in Hydrometallurgy,
ed. G.x. uavies,
24, 238-247.
Li, Y.G., 1988. Metal Solvent Extraction Thermodynamics, Tsinghua University Publishing House (in Chinese).
Pitzer, K.s., 1979. Activity Coefficients in Xlectrolyte Yolution, ed. R.N. Pytkowicz, vol. I, Chap. 7, 157-208.
Teng, T., Y.lr. Li and L.P. Zhang, 1982. Hydrometallurgy,
8:
261-272.
hang, L.P., 'I'.Teng, Y.G. Ai and Z.n. Cheng, 1982. nydrometallurgy, 8. 289-292.

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