Hydrometallurgy 80 (2005) 43 53

www.elsevier.com/locate/hydromet

Data reconciliation and equilibrium constant estimation:

Application to copper solvent extraction
Claude Bazin*, Daniel Hodouin, Mohamed Zouadi
Department of Mining, Metallurgical and Materials Engineering, Laval University, Quebec, Canada
Received 3 September 2004; received in revised form 9 May 2005; accepted 22 June 2005
Available online 9 August 2005

Abstract
Data reconciliation is a proven technique to filter out measurement errors, estimate unmeasured process variables, and
improve the reliability of calculated performance indices. Although data reconciliation techniques are well accepted in mineral
processing, applications to hydrometallurgy processes are not commonly encountered in the literature. This paper shows that
data reconciliation can advantageously be applied to measurements from batch copper solvent extraction tests to improve the
estimation of the extraction chemical equilibrium constant of the process.
D 2005 Elsevier B.V. All rights reserved.
Keywords: Solvent extraction; Equilibrium constant; Data reconciliation; Mass balance

1. Introduction
Solvent extraction of copper is an intermediate
process for the production of copper from oxidised
ore bodies (Biswas and Davenport, 1994). The ore is
leached with sulphuric acid and the produced solution
processed by solvent extraction to concentrate copper
in a rich aqueous phase from which copper is plated
onto cathodes.
The efficiency of a solvent extraction process is
evaluated through flow rate measurements and
assays. For instance measurements of copper contents
* Corresponding author. Tel.: +1 418 656 5914; fax: +1 418 656
5343.
E-mail address: claude.bazin@gmn.ulaval.ca (C. Bazin).
0304-386X/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2005.06.014

in the pregnant solution and in the raffinate are used

to estimate the proportion of copper transferred from
the aqueous to the organic phase. The concentration
of the sulphuric acid in the pregnant and raffinate
solutions as well as a measurement of the copper
content of the organic phase could also be used to
estimate that recovery value (Whewell and Hughes,
1979; Whewell et al., 1979). However the use of
more measurements than required for the estimation
of process performance indices leads to conflicting
results because of unavoidable measurement errors
(Hodouin and Everell, 1985; Crowe, 1996). The
observation of conflicting results should not rule
out the acquisition of redundant data as data redundancy provides a safety net against gross errors and,
when adequately handled, provides a powerful way

C. Bazin et al. / Hydrometallurgy 80 (2005) 4353

H2SO4 content of
pregnant solution (g/l)

44

brium constant and the proposed data reconciliation

approach are described in the following sections.

PS-4

PS-2
PS-0

2. Experimental procedure

PS-1

PS-3

1
1

Cu content of pregnant solution (g/l)

Fig. 1. Factorial design used for the experiments.

to increase the reliability of performance indices

calculated from measurements.
Data reconciliation techniques have been applied
to mineral processing circuits (Hodouin and Everell,
1985), chemical processes (Crowe, 1996) and pyrometallurgical reactors (Bazin et al., 2003) to process
redundant data in the presence of measurement errors.
Applications to hydrometallurgy are not found frequently in the literature. This paper describes the
basis of a data reconciliation technique that could be
applied to process data from batch solvent extraction
tests and continuous operating plants. Two methods
are described. The first data reconciliation technique
uses mass balance constraints only and the second
approach adds a chemical equilibrium constraint to
the reconciliation process.
The paper consists of six sections. The first section
describes the experimental procedure. The second
section analyses the effect of data redundancy and
the third section describes the first approach to reconcile data from solvent extraction tests. A standard
technique for the estimation of the process equili-

Twenty-five solvent extraction tests were conducted

for this investigation following the two-factor factorial
design shown in Fig. 1. The considered factors are the
concentrations of copper and sulphuric acid in the
pregnant solution. Five different ratios of aqueous to
organic volume are used for the extraction tests. Pregnant aqueous solutions were prepared using distilled
water, copper sulphate and sulphuric acid to obtain the
target concentrations of Fig. 1. The organic phase was
prepared by mixing LIX 984 provided by Henkel
Corporation in Orform SX-11 diluent provided by
Chevron Philips to have a 10% v/v concentration of
extractant. The considered volume ratios of organic to
aqueous phase are 5/1, 2/1, 1/1, 1/2 and 1/5.
The copper content of the pregnant solution was
measured by atomic absorption and the sulphuric acid
content was measured by titration with a strong base
(NaOH). Results are shown in Table 1. The measured
sulphuric acid concentration is slightly lower than the
target values of Fig. 1 because the concentration of the
commercial acid was lately found to be lower than
indicated on the bottle. The concentration of sulphuric
acid is measured by titration because the H2SO4 ionic
dissociation into H+ and SO42
is incomplete at the
considered acid concentrations (Yun, 1984; Whewell
and Hughes, 1979; Whewell et al., 1979; Forrest and
Hughes, 1975). A pH measurement can hardly be used
to indicate the acid concentration unless a special
adjustment is made to account for activity change
with the sulphuric acid content (Yun, 1984). In addition, pH measurements in the considered range of acid

Table 1
Aqueous phase composition of the extraction tests (PS = pregnant solution)
Aqueous solution

Pregnant solution
Raffinate 5/1
Raffinate 2/1
Raffinate 1/1
Raffinate 1/2
Raffinate 1/5

PS-0 content (g/l)

PS-1 content (g/l)

PS-2 content (g/l)

PS-3 content (g/l)

PS-4 content (g/l)

Cu

H2SO4

Cu

H2SO4

Cu

H2SO4

Cu

H2SO4

Cu

H2SO4

1.99
0.01
0.03
0.11
0.38
1.22

3.82
6.78
6.61
6.68
6.70
4.73

0.99
0.00
0.00
0.01
0.02
0.19

0.93
2.66
2.29
2.90
2.48
1.97

1.02
0.01
0.02
0.04
0.11
0.41

6.85
8.23
8.27
8.33
8.06
7.82

3.01
0.01
0.04
0.17
0.85
2.03

1.02
5.75
5.78
5.56
4.50
2.63

2.97
0.01
0.09
0.45
1.28
2.24

6.67
11.00
11.34
10.70
9.44
7.81

C. Bazin et al. / Hydrometallurgy 80 (2005) 4353

Table 2
Organic phase composition following the extraction

Fresh organic
Organic 5/1
Organic 2/1
Organic 1/1
Organic 1/2
Organic 1/5

PS-0

PS-1

PS-2

PS-3

PS-4

Cu (g/l)

Cu (g/l)

Cu (g/l)

Cu (g/l)

Cu (g/l)

0.00
0.38
0.96
1.85
3.01
3.56

0.00
0.19
0.49
0.97
1.94
4.01

0.00
0.19
0.50
0.95
1.75
3.00

0.00
0.58
1.41
2.75
4.26
4.91

0.00
0.54
1.36
2.43
3.42
3.72

concentration may be of limited accuracy. For instance,

Doungdeethaveeratana and Sohn (1998) reported a 0.2
error on a pH value of 2.2 or 0.0063 M which yields a
0.004 to 0.01 M range of H+ concentration. Unlike
Whewell and Hughes (1979), the titration was conducted from the initial pH to a pH of 12.0 in spite of
copper hydroxide formation at pH around 4.3. The pH
measurements following titration were processed using
a data reconciliation technique that accounts for copper
hydroxide precipitation (Zouadi, 2003).
The tests were conducted using the standard shakeout technique with separation funnels at constant temperature of 25 F 1 8C. Shaking time was 15 min, which
may not be sufficient to achieve complete equilibrium
(Whewell and Hughes, 1979), but was felt adequate for
this paper demonstration. The sulphuric acid and copper contents of the raffinate were measured, as well as
the copper content of the organic solution following a
2-stage stripping of the solution using a strong acid and
assaying of the obtained aqueous solution. Results of
the tests are given in Tables 1 and 2. It is unusual to
measure the acid content of the raffinate but this measurement increases the data redundancy of the system.
The assaying of copper in the organic phase is less
accurate than the assaying of the aqueous phase as there
are more manipulations and that even a two stage
stripping could not be sufficient to completely extract
the copper. This can be observed in Table 2. However
this data increases the overall problem redundancy.

The extractant molecule is noted RH in Reaction

(1). Alternatively the reaction can be written (Horng
and Maa, 1986):
CuSO4;aq+2 RHorg = H2 SO4;aq + R2 Cuorg

2+
+
Cuaq
+2 RHorg = 2 Haq
+ R2Cuorg.

(1)

(2)

which accounts for the conservation of SO42
. Using

the available measurements the recovery of copper in
the organic phase is calculated as either:
RI

r
xps
Cu;a
xCu;a
xps
Cu;a

RII


Vo xlCu;o
xfCu;o

Va xps
Cu;a

RIII

xrH2 SO4 ;a
xps

H2 SO4 ;a


5

xps
Cu;a

where V stands for a volume, x for the molar concentrations of the subscripted species respectively in
the aqueous (a) and organic phases (o). The superscripts ps, f, r and l stand for pregnant solution, fresh
organic, raffinate and loaded organic. Eqs. (3)(5)
assume volume conservation of the phases during
the test. A fresh organic solution has x fcu;o = 0.
The application of Eqs. (3)(5) leads to the results
of Table 3 for the tests conducted using pregnant
solution PS-0 (see Table 1). Unavoidable measurement errors cause the conflicting results of Table 3
as there should only be one copper recovery for an
extraction test and not three different values. Similar
conflicts can be observed in the results of Tables 14
of Whewell and Hughes (1979) and in Whewell et al.
(1979). Such results are sometimes difficult to handle
and require selecting the variables that should be used
for process evaluation. Data reconciliation is a recogTable 3
Effect of measurement errors on estimated copper recovery (pregnant solution PS-0)

3. Data redundancy analysis

The transfer of copper from the aqueous solution to
the organic phase is usually described by:

45

Extraction
Extraction
Extraction
Extraction
Extraction

5/1
2/1
1/1
1/2
1/5

RI

R II

R III

99.5
98.5
94.5
80.9
38.7

95.5
96.5
93.0
75.6
35.8

96.4
90.8
93.1
93.8
29.6

46

C. Bazin et al. / Hydrometallurgy 80 (2005) 4353

nized approach to deal with redundant and conflicting

information.

solution, so k = 1, 2. . . 5. The estimates of variables

x and q should minimize the quadratic criterion:

Jp x; q

4. Data reconciliation with material balance

constraints

ps
xps
Cu;a;p
yCu;a;p

Data reconciliation is a mathematical technique

that reconciles measurements with a model of the
process from which the measurements originate
(Crowe, 1996; Hodouin and Everell, 1985). The technique is based on the minimization of the weighted
sum of squared residuals subject to constraints derived
from the process model. For the considered solvent
extraction tests the constraints are the copper mass
conservation equation and the stoichiometric constraint of chemical Reaction (2). When the phases
are in equilibrium, the equilibrium conditions provide
additional constraints that should be verified by the
species concentrations.
There are various ways to formulate a data reconciliation problem depending upon the constraints used
and the measured process variables. Two methods are
proposed in this study. In the first approach, only the
constraints of mass conservation for Cu and SO42
are
enforced. The considered measurements are the phase
ratio, the copper and sulphuric acid contents of the
aqueous phase and the copper content of the organic
phase. Since there are no common variables or constraints in the tests for each of the initial pregnant
solutions the data can be reconciled independently for
the five different systems of PS-0, PS-1, PS-2, PS-3
and PS-4. The addition of a constraint for the chemical equilibrium will create a link between the tests
with the various pregnant solutions as it is shown in a
subsequent section.
The molar conservation constraints are written:
f
r
l
xps
Cu;a;p qk xCu;o;k;p xCu;a;k;p qk xCu;o;k;p


ps
r
r
xps
Cu;a;p xH2 SO4 ;a;k;p
xH2 SO4 ;a;p xCu;a;k;p

The subscript k is used to indicate one of the n

extraction tests conducted with a given pregnant solution p, and q k stands for the volume ratio of organic to
aqueous phase for extraction k. In this study, 5 extraction tests are conducted using the same pregnant

2

rypsCu;a;p
ps
xps
H2 SO4 ;a;p
yH2 SO4 ;a;p

2

rypsH SO ;a;p
2 4
2  r

n 
X
xCu;a;k;p
yrCu;a;k;p 2
qk
rk

rrk
ryrCu;a;k;p
k1
 k

xH2 SO4 ;a;k;p
yrH2 SO4 ;a;k;p 2

ryrH SO ;a;k;p
2 4
 l

xCu;o;k;p
ylCu;o;k;p

8
ryl
Cu;o;k;p

where y stands for the measured value of the generic

variable x, r the measured phase ratio and n the
r
number of extraction tests. For instance x Cu;a;k;p
is
the estimated aqueous molar concentration of copper
in the raffinate of extraction k using the pregnant
r
solution p, and y Cu;a;k;p
is the corresponding measured
value. If it is assumed that the measurement errors
obey zero-mean normal distribution and are not correlated, the criterion of Eq. (8) corresponds to the
maximum likelihood estimation of the process variables under the exact constraints of Eqs. (6) and (7).
The weighting by the inverse of the measurement
error standard deviation (r) imposes to have an estimated value of a reliable measurement close to the
corresponding measurement, otherwise the criterion
value would increase significantly (Bazin et al.,
2005; Hodouin and Everell, 1985).
The minimization of Eq. (8) with respect to the
phase ratios and species concentrations subject to the
constraints of Eqs. (6) and (7) is performed using
initial guesses for the search variables, selected as
ps
the pregnant solution composition (x Cu;a;p
and
ps
x H2SO4;a;p), the phase ratio (q k ) and the copper content
r
of the raffinate (x Cu;a;k;p
). The copper content of the
organic phase and the sulphuric acid concentration in
the raffinate are then obtained from the search variable
using the constraints of Eqs. (6) and (7):
xlCu;o;k;p

r
xps
Cu;a;p
xCu;a;k;p

qk

C. Bazin et al. / Hydrometallurgy 80 (2005) 4353


ps
r
xrH2 SO4 ;a;k;p xps


x
Cu;a;k;p xH2 SO4 ;a;p :
Cu;a;p

10

These values are inserted into the criterion of Eq.

(8) together with the search variables values. The
criterion is minimized by adjusting the values of the
search variables using a non-linear optimization
search algorithm, such as Solver in Excel Microsoftk. A fresh organic solution with a zero copper
content is assumed for the reconciliation. Several
starting points were used for the non-linear optimization in order to ensure that the obtained solution was
not a local minimum.
The application of the data reconciliation procedure to the tests conducted with pregnant solution PS0 led to the results given in Table 4. The standard
deviations in Eq. (8) were calculated by using a 5%
relative error for the assays of copper in the aqueous
phase, 10% for the copper assays in the loaded
organic phase, 15% for the sulphuric acid content,
and 5% for the organic to aqueous ratios. Because
of the lower standard deviation associated to the
measured copper content of the aqueous solution,
the reconciled values for this variable are closer to
the measured values compared to results for sulphuric
acid or organic copper concentrations (see Table 4).
The estimated phase ratios remain practically equal to
experimental ratios. The same observation is made for
the reconciliation of the other pregnant solutions data
showing that it is not necessary to include the phase
ratio for batch extraction tests in the data reconciliation search.
Since reconciled values verify the material conservation equations, the same copper recovery is
obtained with any of the reconciled variables. This
property of the reconciled values eliminates the need

47

Table 5
Recovery of copper calculated from raw and reconciled data (PS-0)

Extraction
Extraction
Extraction
Extraction
Extraction

5/1
2/1
1/1
1/2
1/5

RI

R II

R III

R R1

99.5
98.5
94.5
80.9
38.7

95.5
96.5
93.0
75.6
35.8

96.4
90.8
93.1
93.8
29.6

99.49
98.46
94.35
80.44
36.95

R I, R II, R III: Calculated using Eqs. (3)(5).

R R1: Calculated using reconciled data.

for the subjective selection of variables for the recovery calculation. The recoveries obtained using the
reconciled data are given in Table 5. Although the
estimated recoveries are close to the values observed
with the measured copper assays (R I from Eq. (3)) it
will be shown in a following section that their estimated standard deviation is lower than that obtained
when calculated from measurements.

5. Estimation of the extraction equilibrium

constant
The described data reconciliation provides a way to
estimate assays that verify mass conservation and
stoichiometric constraints for extraction tests conducted with a given pregnant solution. Since the
tests are conducted at constant temperature for a
sufficiently long reaction time to suppose that a thermodynamic equilibrium between the organic and aqueous phases is reached, one can define the following
equilibrium constant for Eq. (1):
2

CuR2 org H aq

Ke


RH2org Cu2 aq

11

Table 4
Comparison of measured and reconciled data for PS-0 extraction tests
Aqueous solution

Pregnant
5/1
2/1
1/1
1/2
1/5

Loaded organic

Cu content (g/l)

H2SO4 (g/l)

Cu content (g/l)

Phase ratio

Measured

Reconciled

Measured

Reconciled

Measured

Reconciled

Measured

Reconciled

1.99
0.01
0.03
0.11
0.38
1.22

1.95
0.01
0.03
0.11
0.38
1.23

3.82
6.78
6.61
6.68
6.70
4.73

3.81
6.80
6.77
6.64
6.22
4.92

0.38
0.96
1.85
3.01
3.56

0.39
0.96
1.84
3.13
3.59

0.5000
2.0000
1.0000
0.5000
0.2000

0.5004
1.9998
0.9997
0.5001
0.2001

48

C. Bazin et al. / Hydrometallurgy 80 (2005) 4353

which assumes an Henryan behaviour, or constant

activity coefficients and appropriately selected standard states, for both phases.
The H+ concentrations are estimated from the
sulphuric acid concentration using the dissociation
reactions:
H2SO4 = HSO4
+ H+

(12)

HSO4
= H+ + SO42
.

(13)

The dissociation constant of the first reaction is

large enough to assume a complete dissociation into
HSO4
. The second reaction has a dissociation constant of 0.0125 (Zouadi, 2003) and is not complete for
the range of sulphuric acid concentration used for the
extraction tests (Whewell and Hughes, 1979).
The calculated equilibrium constants using the
reconciled data from Table 4 are given in Table 6.
Because of the sensitivity to measurement errors, the
calculated equilibrium values vary significantly
around an average value of approximately 17.4. The
concentration of the extractant (RH) in the fresh
organic phase was approximated at 0.16 M for the
calculations of the equilibrium constant (Hoh et al.,
1989). Unfortunately the authors were not aware of
accurate methods to measure the actual active extractant concentration.
The variation of the calculated chemical constants
is mainly due to measurement errors that are not
completely removed by data reconciliation. The variation could also be attributed to a higher than considered variation in free active hydroxyl oxime
content of the extractant solution. A non-Henryan
behaviour of activities (Forrest and Hughes, 1975)
could also be responsible for that variation, although
subsequent results will not support that hypothesis.

Table 6
Equilibrium constants calculated from reconciled data
Ratio Org./Aq.

5/1
2/1
1/1
1/2
1/5

Pregnant solution
PS0

PS1

PS2

PS3

PS4

11.0
11.7
9.5
11.6
4.7

4.3
12.3
12.2
13.6
14.6

10.8
12.5
12.7
12.6
13.5

11.1
13.2
13.9
22.4
69.2

91.8
17.7
11.4
9.6
6.6

Table 7
Sensitivity of the estimated equilibrium constant to extractant concentration and sulphuric acid dissociation (pregnant solution PS-0)
Ratio
Org./Aq.

H2SO4 dissociation

Extractant concentration (M)

Partial

Complete

0.16

0.14

0.18

5/1
2/1
1/1
1/2
1/5

11.0
11.7
9.5
11.6
4.7

34.1
36.1
29.4
35.2
13.5

11.0
11.7
9.5
11.6
4.7

14.7
16.3
14.7
25.5
14.2

8.5
8.8
6.7
6.6
2.3

Table 7 shows the effect of the assumption of a

complete dissociation of sulphuric acid into H+ and
SO42
, and of the selected organic phase molar concentration on the calculated equilibrium constant.
Only the results for PS-0 are presented in Table 7.
As expected the calculated equilibrium constant is
sensitive to the proper handling of the sulphuric acid
dissociation. The equilibrium constants calculated
using extractant concentrations of 0.14 and 0.18 lead
to a variation of more than 25% of the obtained values
with 0.16 M. Considering that the determination of
the free active extractant is a tricky matter this may
explain some of the scattering of the equilibrium
constant values found in the literature (Aminian and
Bazin, 2000).
A common practice (Aminian and Bazin, 2000) to
estimate the equilibrium constant is to use a regression
over the logarithm of Eq. (11) organized as:

log

CuR2 org
 2 
Cu aq

!
logKe
2log

H aq
RHorg

!
:
14

Eq. (14) describes a straight line with a slope of

2 and a Y axis intersection at log(K e). The plot of
all the reconciled data for the considered extraction
tests is shown in Fig. 2. The observed linear trend
confirms that the data belongs to the Henryan
domain. The application of a standard linear regression to this data yields a slope of
1.7 and a value
of K e of 14.0. The choice of the fresh organic
extractant concentration has an effect on the estimated slope. For instance the use of a fresh extractant concentration of 0.17 M instead of 0.16 M
yields a slope of
1.99 and an equilibrium constant
of 9.7.

Log(CuR2/Cu 2+).

C. Bazin et al. / Hydrometallurgy 80 (2005) 4353

49

3,0

6. Data reconciliation with mass conservation and

extraction equilibrium constraints

2,0

Since for the considered extraction tests the temperature was kept fairly constant, the tests conducted
with the 5 pregnant solutions should yield a unique
value for the equilibrium constant. The five series of
tests could thus be linked by the additional constraint
of a unique equilibrium constant and the data reconciliation could be applied to the 25 tests simultaneously (5 pregnant solutions and 5 organic to
aqueous ratios). The criterion of Eq. (8) is then

1,0

With reconciled data

0,0
-1

-0,5

0,5

Log(H+/RH)
Fig. 2. Estimation of the equilibrium constant.

Initial guess for the equilibrium

constant

p=1

Initial guesses for the composition of

pregnant solution p

Modify pregnant
solution
composition
(NLOA)

Calculation of raffinate and organic

solution composition for each extraction
with pregnant solution p

Calculation of pregnant solution p

criterion (Jp)

p=p+1
No
Jp=Minimum?
Modify equilibrium
constant (NLOA)

Yes
No
p=nps
Yes
Calculation of the total criterion

No
Jtot=Minimum?
Yes
Solution
Fig. 3. Search procedure for the data reconciliation with estimation of equilibrium constant (NLOA= Non Linear Optimization Algorithm).

50

C. Bazin et al. / Hydrometallurgy 80 (2005) 4353

extended to the 5 pregnant solutions, and the parameters to be estimated augmented by K e:


ps
ps
ps
;
x
;
N;
x
;
x
Jtat Ke ; xps
Cu;a;1 H2 SO4 ;a;1
Cu;a;nps H2 SO4 ;a;nps

nps
X

15

Jp

p1

where J p is given by Eq. (8) and J tot is minimized by

the hierarchical search procedure depicted in Fig. 3.
The search algorithm is fed with initial guesses for the
ps
equilibrium constant (K e) and composition (x Cu;a;p
;
ps
x H2SO4;a;p) of the pregnant solution p to estimate the
copper concentration of the raffinate of extraction k
by solving the non-linear equation for xrCu2 ;a;k;p :
 xps
2

xrCu2 ;a;k;p 

Cu2 ;a;p
xrH ;a;k;p
rk
Ke

2

xps 2
xr 2
xrCu2 ;a;k;p xfRH;o
2 Cu ;a;p rk Cu ;a;k;p
16
where:
xrH ;a;k;p xrH2 SO4 ;a;k;p z xps
H2 SO4 ;a;p



ps
r
xCu2 ;a;p
xCu2 ;a;k;p z

17

with z the SO42
concentration due to the dissociation

of the HSO4
which should verify the second dissociation constant for Eq. (16):






ps
r
xrCu2 ;a;k;p z xps
H2 SO4 ;a;p xCu2 ;a;p
xCu2 ;a;k;p z



0:0125
ps
r
xps
H2 SO4 ;a;p xCu2 ;a;p
xCu2 ;a;k;p
z





xrSO2
;a;k;p xrH ;a;k;p
4




18
xrHSO
;a;k;p

where xrCu2 ;a;k;p z includes the SO42
of the CuSO4,

assuming a complete dissociation of this sulphate. The
estimated
 equilibrium concentration of copper

r
xcu2 ;a;k;p is used to calculate the raffinate sulphuric
acid concentration and copper content of the organic
phase allowing the calculation of the corresponding
pregnant solution criterion ( J p). The criterion value is
passed to a non-linear optimization algorithm that
modifies the composition of the pregnant solution
until the criterion J p of Eq. (8) is minimized. Once
the procedure has been applied to the n ps considered
pregnant solutions, the J p criteria are summed up to
obtain the total criterion value Eq. (15) used to feed a
non-linear optimization algorithm that searches the
optimum value for the equilibrium constant.
Results of the application of the data reconciliation technique for the extractions conducted with
pregnant solution PS-0 are given in Table 8. The
phase ratios are not included in the reconciliation
since earlier results show that this was not necessary
for the considered test data. The equilibrium constant was estimated at 13.8, a value consistent with
a previous estimation (Aminian and Bazin, 2000). A
0.16 M concentration of fresh extractant concentration is used for the reconciliation. The estimation of
the equilibrium constant remains sensitive to the
extractant concentration of the fresh organic solution
with variation in the order of 20% for a F 0.02 M
variation of extractant concentration. However the
data reconciliation algorithm could be easily modified to incorporate the extractant concentration in
the list of search variables. Such procedure led to an
estimated extractant concentration of 0.165 M while
the equilibrium constant decreased from 13.8 to
12.4 and the overall criterion Eq. (15) from 77.0
to 74.7.

Table 8
Measured and reconciled concentrations for PS-0 using data reconciliation with equilibrium constant estimation
Aqueous solution

Loaded organic

Cu content (g/l)

PS-0
5/1
2/1
1/1
1/2
1/5

H2SO4 (g/l)

Cu content (g/l)

Measured

Reconciled

Measured

Reconciled

Measured

Reconciled

1.99
0.01
0.03
0.11
0.38
1.22

1.954
0.009
0.028
0.089
0.402
1.200

0.099
0.001
0.002
0.006
0.019
0.061

3.82
6.78
6.61
6.68
6.70
4.73

4.11
7.11
7.08
6.99
6.50
5.28

0.573
1.017
0.992
1.002
1.005
0.710

0.38
0.96
1.85
3.01
3.56

0.389
0.963
1.865
3.105
3.793

0.038
0.096
0.185
0.301
0.356

C. Bazin et al. / Hydrometallurgy 80 (2005) 4353

The reconciled values obtained with this approach

deviate more from the measured values than those
obtained from the data reconciliation using only
mass conservation. This result was anticipated
because of the strong constraint imposed by the
unique equilibrium constant. The estimated and
observed concentrations for all the tests and pregnant
solutions are compared in Fig. 4. Results of Fig. 4
clearly show the presence of a gross error for one
measurement. The indicated data (Fig. 4) corresponds
to the 5/1 extraction test for PS-4 which yields a 0.005
g/l copper in the raffinate that is reconciled to 0.029 g/
l. This adjustment is consistent with other extraction
results. Indeed the 0.005 g/l measurement is significantly lower than the 0.012 g/l of copper for the 5/1
extraction conducted with PS-3 which has a lower
sulphuric acid content compared to the PS-4 pregnant
solution. The higher pH of PS-3 compared to PS-4
should be favourable to the copper extraction and of a
lower copper content at equilibrium conditions.
This example shows that data reconciliation provides an efficient way to detect gross errors in a
data set. In practice the weight of the measurement
that contains the gross error should be revised by
increasing the associated standard deviation and
repeating the data reconciliation procedure. This
would allow more deviation between the measurement and the reconciled value without significantly
affecting the criterion (Eq. (15)) and the effort
made for reconciling the other measurements. The
adjusted sulphuric acid concentrations are not systematically lower than the observed ones, but there is a
trend that may indicate an inaccuracy in the titration
procedure. The adjustments remain within the experi-

Table 9
Recovery of copper calculated using raw and reconciled data (PS-0)

Extraction
Extraction
Extraction
Extraction
Extraction

R II

R III

R R1

R R2

99.5
98.5
94.5
80.9
38.7

95.5
96.5
93.0
75.6
35.8

96.4
90.8
93.1
93.8
29.6

99.49
98.46
94.35
80.44
36.95

99.56
98.59
95.47
79.44
38.82

mental error associated with the sulphuric acid concentration measurements.

The estimated copper recoveries for the 5 extraction tests conducted with pregnant solution PS-0 are
given in Table 9. Despite the more important adjustments due to the additional constraint, the estimated
recoveries remain fairly close to the previously estimated values. The method could also be adapted to
include the parameters of a semi-empirical model
(Horng and Maa, 1986). An important advantage
associated with the data reconciliation procedure is
related to the reduction of the standard deviation of
the calculated recoveries as it is shown in the next
section.

7. Accuracy of performance indices

The performance of a reactor is usually measured
through indices calculated from measurements or
reconciled data. Measurements, as well as reconciled
12

Reconciled H2SO4 (g/l) .

Reconciled Cu2+ (g/l).

5/1
2/1
1/1
1/2
1/5

RI

R I, R II, R III: Calculated using Eqs. (3)(5).

R R1: Calculated using reconciled data with mass conservation
constraints.
R R2: Calculated using reconciled data with equilibrium constant and
mass conservation constraints.

10
1
Gross error

0,1
0,01
0,001
0,001

51

0
0,01

0,1

Measured

Cu2+

(g/l)

10

Measured H2SO4 (g/l)

Fig. 4. Measured and reconciled data for all tests.

12

52

C. Bazin et al. / Hydrometallurgy 80 (2005) 4353

Table 10
Standard deviations of performance indices (PS-0)

Extraction
Extraction
Extraction
Extraction
Extraction

5/1
2/1
1/1
1/2
1/5

RI

rr

R R1

rr

R R2

rr

99.5
98.5
94.5
80.9
38.7

0.036
0.077
0.293
1.182
8.065

99.5
98.5
94.4
80.4
37.0

0.020
0.071
0.244
0.960
6,750

99.6
98.6
95.5
79.4
38.8

0.005
0.030
0.157
0.441
0.876

R I: Calculated using Eq. (3).

R R1: Calculated using reconciled data with mass conservation constraints.
R R2: Calculated using reconciled data with equilibrium constant and
mass conservation constraints.

data, are estimates of the true values of variables and

as such they contain errors that propagate through the
calculations of the performance indices that will also
exhibit a statistical distribution. However reconciled
data have lower standard deviation than measured
data and exhibit covariance due to the constraint
imposed for their estimation (Hodouin et al., 1989)
which is a favourable factor for the estimation of
reliable performance indices.
The copper recoveries for pregnant solution PS-0
calculated using measured and reconciled data with the
associated relative standard deviation are given in
Table 10. The relative standard deviation is obtained
from:
rR
rrR
19
R
where r R is the standard deviation of the copper recovery (R) calculated using an error propagation method
and a Monte Carlo simulation (Zouadi, 2003). Results
of Table 10 show that the use of reconciled data instead
of measurements significantly reduces the standard
deviation of the calculated performance indices. Reliable performance indices could advantageously be
used for process optimization such as the analysis of
the factorial design experiments conducted here in
order to establish principal and interaction effects that
could be used to identify the optimum operating conditions for the extraction.

8. Conclusion
Two data reconciliation techniques are described to
process measurements obtained from batch solvent
extraction tests. The techniques are applied to redun-

dant data in order to produce consistent data with

mass conservation and chemical equilibrium constraints. In addition to producing consistent information, data reconciliation provides an efficient way to
detect gross experimental errors and to obtain reliable
performance indices.
The data reconciliation technique described in this
paper includes the estimation of consistent extraction
equilibrium constant and reconciled measurements.
The application of the data reconciliation to the
copper solvent extraction tests with LIX-984 in
Orform SX-11 yielded an equilibrium constant of
12.4. Results however show that the estimated equilibrium constant is strongly dependent of the value
used for the extractant concentration of the fresh
organic solution.

Acknowledgments
The authors are grateful to Henkel Corporation and
Chevron Phillips for supplying the reagents used for
the tests. The authors acknowledge the financial support of the Natural Science and Engineering Research
Council of Canada and the Research Team Program of
the Province of Quebec.

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