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
(D2EHPA)-nC7H16-Cos04-CuS04-H2S04
and listed.
the component
A new thermodynamic
activity
coefficients
in quaternary
systems.
chemical
reactions
involved
equilibrium
he-
system
ternary
constants
VLE
for two
in the extraction
termined.
INTRODUCTION
The metal solvent
in nuclear
industry
and automatic
extraction
and hyorometallurgy.
The process
distribution
used
design
an0 activity
equation
equation
extraction
systems.
distribution
proposed
constants
function
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.
a new molecular
be predicted
cently Ji-ding
to correlate
sine curve
in organic
for ternary
and
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)
extraction
system, which
in hydrometallurgy.
to D2EHPA-nC7H16-Cos04
is important
in Co and Cu
EXPERIMENTAL
Reagents
--D2EHPB
(di(2-ethyl
CH2)2P04H))
hexyl)
phosphoric
acid
(CH~(CH~)TCH(L~H~)
used as extractant
Metal
were synthesized
of D2EHPA.
and purified.
Normal heptane
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
two liquia
After reaching
by centrifugal.
Analytical
Instrument
space sampler
schematic
by the Beijing
(made by American
diagram
(produced
Hewlett-Packard
of the experimental
head-
Company).
equipment
is shown in Fig
solutions
with different
solutions
tial concentrations
concentrations
of D~EHPA-C~HI~
of D2EHPA
of Co+304 and
with different
0.68,
ini-
0.725
and
of experiments
including
53
equilibrium
initial
concentration
of D2EHPx
concentration
in organic
in aqueous
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~
The thermodynamic
may be written
equilibrium
constants
as follows:
(2)
(3)
for mixed
electrolyte
the individual
solution
ionic activity
coefficient
for iOn
i (Vi) in aqueous
in electrolyte
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_
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+
of component
of pure liquia
component
as the mixed
solution).$i
mole fraction
of liquid
i in solution
component
parameters
anu pressure
fraction
i in solution.
between molecules
and
(4) all the Aij and Bij have been given from the corresponuing
three bi_nary VLE systems
C~H~~-CU(HR~)~*~H~O
systems),
are in agreement
than 1.59.
The remaining
relative
three binary
coefficient
of
data
for f, is less
0f
interaction
have t0 predict
non-volatile
parameters
the dctivity
components
for further
coefficient
by use 0f Gibbs-Duhem
equili-
Differentia-
Table
ecules
equation
SO we
combin-
parameters
between
mol3~ Interaction
(Aijand Bij)at 25C
tant pressure
HA
and temperature,
we get:
Co(HW,
.2H,O
CuWR,),
.2&O
-0.1362
-03049
-2.456
equation for
organic phase
is as follows;
x,dlnf,+
calculation.
x2dlnf;+
x3dlnf;+
dlnfi = 0
Eere the star (*) denotes
x4
(7)
the
-5.729
H,R,
a4039
241
infinite
dilution
convenience.
From Eq.(5),(6)
and
as reference
state fop
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
The thermodynamic
reactions
equilibrium
can be obtained
in Table 2.
in the organic
constants
simultaneously.
concentration
concentrations
dissolved
are listed
of saturation
of metals
phase
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
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
concentration
C"
C20
f
of this reoear-
Science Founda'ion.
in molarity
activity coefficient
ference state
solution
in mo-
242
activity coefficient
reference state
ionic strength
in aqueaus
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.