Minerals Engineering 22 (2009) 13501358

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Dynamic modelling of copper solvent extraction mixersettler units

C.M. Moreno a, J.R. Prez-Correa a,*, A. Otero b
a b

Department of Chemical and Bioprocesses Engineering, Ponticia Universidad Catlica de Chile, Casilla 306, Santiago 22, Chile Mining Centre, Ponticia Universidad Catlica de Chile, Casilla 306, Santiago 22, Chile

a r t i c l e

i n f o

a b s t r a c t
The copper Leaching, Solvent Extraction and Electrowinning circuit (LXSXEW) is one of the most effective processes for extracting copper from low grade ores. This work focuses on the liquidliquid extraction SX sub-process, since many difcult to handle operational problems within LXSXEW circuits are related to SX malfunction. Controlling these problems better can reduce operational costs and increase recovery and copper production. Realistic dynamic simulation is a standard tool nowadays to design and assess more effective control strategies. In this work we present a general dynamic model for SX mixersettlers, and applied it to two different units, one located in an extraction stage and the other in a stripping stage of a copper plant. The model includes a non-trivial settler hydrodynamics represented by a set of nonlinear differential equations for both mixer and settler units. The mixer is modelled as a continuous stirred tank reactor and the settler as a hydrodynamic circuit combining series and parallel connections of continuous stirred tank and plug ow reactors. The model was calibrated with industrial plant data, resulting in realistic simulations of outlet copper concentrations. Using the proposed model, we obtained better tting than that achieved with simpler settler models that include only a time delay. The model tting parameters provide sufcient exibility to accurately reproduce the dynamics of different units in industrial plants. 2009 Elsevier Ltd. All rights reserved.

Article history: Received 30 January 2009 Accepted 4 September 2009 Available online 7 October 2009 Keywords: Extractive metallurgy Hydrometallurgy Simulation

1. Introduction Due to increasing copper world demand, there is a strong incentive to apply different processes to copper extraction from low grade ores. The copper Leaching, Solvent Extraction and Electrowinning circuit (LXSXEW) (see Fig. 1) is one of the most effective processes for this purpose. In this work, we focus on the liquidliquid extraction SX process, since many of the difcult to handle operational problems within this circuit are related to SX malfunction. Critical problems normally found in SX plants, which have a considerable impact in extraction efciency and selectivity, are: crud formation, organic and aqueous phase entrainments, and variable and unpredictable phase separation times in the settlers (Bergh and Yianatos, 2001). For example, uncontrolled organic and aqueous ow-rates may cause inefcient phase separation, leading to entrainment and process instability. These, in turn, reduce cathodes quality, increase the consumption of valuable chemicals, contaminate the electrolyte solutions, cause premature corrosion of expensive anodes and increase organic phase losses. Additionally, copper concentration and pH are usually sampled and regulated manually by operators. Since the samples are analyzed in the laboratory, taking 4 h
* Corresponding author. Tel.: +56 3544258; fax: +56 3545803. E-mail address: perez@ing.puc.cl (J.R. Prez-Correa). 0892-6875/$ - see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.mineng.2009.09.003

in average, it is not surprising that process regulation is poor. As a result, strong disturbances are unavoidable and many of them may pass unnoticed and uncontrolled for at least 4 h. Hence, it can be argued that many of the SX operational problems are related to the lack of effective monitoring and control systems specic for this process. Consequently, on-line measurement of copper concentrations in the main process streams together with an effective automatic control strategy, should stabilize the process, improve cathodes quality and homogeneity, and reduce operational costs. Unfortunately, it is not possible to measure on-line copper concentrations with affordable and reliable instrumentation. In addition, it is expensive and risky to develop and test control strategies directly in the process plant. Alternatively, dynamic simulation can be used effectively to develop and test estimation and control strategies before they are implemented on-line, reducing the risks of catastrophic operational events, and the time and costs of development. Despite that several SX process models have been presented in the literature, many of them are steady state or either too simple to represent realistic industrial data or too complex to calibrate. Moreover, there are still many phenomena in SX processes that are not well understood. For example, Van Bochove et al. (2000) developed a thermodynamic model that predicts exactly the isotherms of equilibrium. However, this model is very complex and

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Nomenclature A a1A a1O a2A a2O B b1A b1O b2A b2O f C D KE KS Qai QAL Qam QAUi Qoi QOL Qom QOUi VAL1 VAL2 Vam VAUi VOL1 VOL2 Vom VOUi VS X* Xi Xa L1 Xb L1 extraction equilibrium isotherm parameter (g L1) aqueous active zone fraction of rst CholetteCloutier unit organic active zone fraction of rst CholetteCloutier unit aqueous active zone fraction of second CholetteCloutier unit organic active zone fraction of second CholetteCloutier unit extraction equilibrium isotherm parameter (g L1) aqueous dead zone fraction of rst CholetteCloutier unit organic dead zone fraction of rst CholetteCloutier unit aqueous dead zone fraction of second CholetteCloutier unit organic dead zone fraction of second CholetteCloutier unit plug ow fraction of slow owing branch stripping equilibrium isotherm parameter stripping equilibrium isotherm parameter (g L1) extraction mass transfer coefcient (h1) stripping mass transfer coefcient (h1) aqueous mixer inlet owrate (m3 h1) aqueous owrate in slow ow branch in settler (m3 h1) aqueous mixer outlet owrate (m3 h1) aqueous owrate in ith CSTR outlet in fast ow branch in settler (m3 h1) organic mixer inlet owrate (m3 h1) organic owrate in slow ow branch in settler (m3 h1) organic mixer outlet owrate (m3 h1) organic owrate in ith CSTR outlet in fast ow branch in settler (m3 h1) aqueous volume of rst CholetteCloutier unit (m3) aqueous volume of second CholetteCloutier unit (m3) aqueous volume in mixer (m3) aqueous volume of ith CSTR (m3) organic volume of rst CholetteCloutier unit (m3) organic volume of second CholetteCloutier unit (m3) organic volume in mixer (m3) organic volume of ith CSTR (m3) settler volume (m3) aqueous equilibrium copper concentration (g L1) aqueous inlet copper concentration (g L1) aqueous copper concentration in active zone of rst CholetteCloutier unit (g L1) aqueous copper concentration in dead zone of rst CholetteCloutier unit (g L1) Xa L2 Xb L2 Xm XP X ST XUi Y* Yi Ya L1 Yb L1 Ya L2 Yb L2 Ym YP Y ST YUi aqueous copper concentration in active zone of second CholetteCloutier unit (g L1) aqueous copper concentration in dead zone of second CholetteCloutier unit (g L1) aqueous copper concentration in mixer (g L1) time delayed aqueous copper concentration in slow ow branch (g L1) aqueous equilibrium copper concentration in stripping stage (g L1) aqueous copper concentration in ith CSTR in fast ow branch in settler (g L1) organic equilibrium copper concentration (g L1) organic inlet copper concentration (g L1) organic copper concentration in active zone of rst CholetteCloutier unit (g L1) organic copper concentration in dead zone of rst CholetteCloutier unit (g L1) organic copper concentration in active zone of second CholetteCloutier unit (g L1) organic copper concentration in dead zone of second CholetteCloutier unit (g L1) organic copper concentration in mixer (g L1) time delayed organic copper concentration in slow ow branch (g L1) organic equilibrium copper concentration in extraction stage (g L1) organic copper concentration in ith CSTR in fast ow branch in settler (g L1) extraction stage organic copper concentration steady state gradient (g L1) stripping stage aqueous copper concentration steady state gradient (g L1) extraction efciency coefcient stripping efciency coefcient fraction of aqueous solution owing by slow ow branch in settler fraction of organic solution owing by slow ow branch in settler aqueous exchange rate between zones in rst Cholette Cloutier unit organic exchange rate between zones in rst Cholette Cloutier unit aqueous exchange rate between zones in second CholetteCloutier unit organic exchange rate between zones in second CholetteCloutier unit

eE eS gE gS
uA uJ k1A k1O k2A k2O

requires a great deal of specic experimental information, not normally found in an industrial environment. Using simple isotherms calibrated with plant data, Aminian et al. (1998) obtained good

Fig. 1. Typical LXSXEW copper plant.

predictions of the steady states of a test SXEW plant. The mixer was modelled as an ideal continuous stirred tank reactor, hereinafter, CSTR, and the settler as two compartments in parallel, an ideal plug ow and an ideal CSTR. Using a more elaborated steady state model, Pinto et al. (2004) improved the conguration of an SX Cu plant applying multi-objective optimization. They included chemical reaction kinetics and a non-ideal hydrodynamics in the mixer settler units. Then a multi-variable optimizing objective function was dened that considered equipment geometry, residence time and agitator speeds, among other design parameters. The optimization yielded the optimum unit and plant design, which can be applied for the design of new plants, or for improving existing designs. In spite of being extremely useful in SX plant design, that model cannot be used to develop and test control systems. Only dynamic models are useful to design control strategies by simulation. Most of these models presented in the literature

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include simple thermodynamics and rate expressions, where most of the complexity is lumped into the hydrodynamics of the settler. An example of this is the mixersettler cascade model for rare earths of Wichterlov and Rod (1999). Here, the hydrodynamics were modelled as a series of CSTRs. However, this model is not that useful to design control systems since it is too simple, not able to reproduce the complex dynamics observed in real plants. Wilkinson and Ingham (1983) and Ingham et al. (2007) modelled the mixer as a CSTR, but included entrainment factors in the outlet streams. Furthermore, the settler was modelled as two parallel compartments, just as in the Aminian model. Although this is an improvement over Wichterlov and Rod model, no comparison with industrial data has been presented so far. Komulainen et al. (2006) presented a dynamic model of a SX Cu process calibrated with plant data, however, the settler is modelled simply as a delay. Hence, even though the model described the SX process dynamics well, it will probably be difcult to t that model to other plants with more complex behaviour. Here, we present a exible SXCu unit model, able to reproduce the complex dynamics observed on any stage at any industrial plant. The model includes McCabeThiele specic diagrams and complex settler hydrodynamics. The model considers variables normally measured at industrial facilities and simulates the dynamic response of copper concentrations in both phases in the outlet streams.

2.1. Mass balances The model was obtained by applying independent copper and total mass balances on the mixer and the settler (Fig. 2) under the following assumptions:  Mass transfer in the settler is signicantly lower than in the mixer, therefore mass transfer is considered only in the mixer (Wilkinson and Ingham, 1983).  Equilibrium isotherms dene composition gradients for mass transfer (Steiner and Hartland, 1983).  Perfect mixer (Wilkinson and Ingham, 1983).  Entrainments only occur in the settler (Aminian et al., 1998).  Settler modelled with non-ideal hydrodynamics (Ingham et al., 2007).  Constant density.

2.1.1. Mixer balances Applying total mass balances (see Fig. 2) to both, aqueous and organic phases in the mixer tank, yield,

dV Am Q Q Om V Am Q Ai Am V Am V Om dt dV Om Q Q Om Q Oi Am V Om V Am V Om dt

1 2

2. Process model Fig. 1 (Jackson, 1986) describes a standard LXSXEW industrial plant. Leaching (LX) is the rst stage, where copper is extracted by washing the ore with an acid aqueous solution (SX rafnate). The outlet stream of LX, the pregnant liquid solution (PLS), is the inlet stream to the rst stage of the SX process (extraction). In this stage, the PLS stream is mixed with the barren organic solution (BO), i.e., the outlet stream of the second SX stage (stripping), to selectively transfer copper from the aqueous phase to the organic phase. The outlet loaded organic solution (LO) from the extraction stage, is mixed in the stripping stage with the lean electrolyte (LE) stream coming from the electrowinning process. Since there is a different pH in the stripping stage, copper transfers now from the organic phase to the aqueous phase. Then, the outlet aqueous stream from the stripping stage, rich electrolyte (RE), goes to the electrowinning stage, where copper is extracted in cathodes, bringing the lean electrolyte back to the loop. In this work we developed a general dynamic model for mixer settlers and t it to two different units, one in the multi-units extraction stage and the other in the multi-units stripping stage of an SX process of a LXSXEW copper plant from Molymet S.A., similar to that shown in Fig. 1. Although, this plant, with an annual production of 1 million lb of copper, is rather small compared to other industrial mining facilities.

copper balances differ if the tank is in an extraction or in a stripping stage. For an extraction unit,

dX m Q Ai X i X m K E Y Y m E dt V Am dY m Q Oi Y i Y m K E Y Y m E dt V Om
and for a stripping unit,

3 4

dX m Q Ai X i X m K S X X m S dt V Am dY m Q Oi Y i Y m K S X X m : S dt V Om

5 6

In these equations, QAi and QOi are the aqueous (subindex A) and organic (subindex O) mixer inlet owrates, VAm and VOm are the aqueous and organic volumes in the mixer, Xm and Ym are the copper concentrations in the aqueous and organic phases in the mixer, respectively, KE and KS are the copper mass transfer coefcients in the extraction and stripping units (subindex E stands for extraction and S for stripping). X and Y are pseudo-equilibrium copper concentrations deS E ned by empirical equilibrium isotherms (X* or Y*) and extraction efciencies (gE or gS) (Wilkinson and Ingham, 1983).

Y 1 gE Y i gE Y E X 1 gS X i gS X S

7 8

Fig. 2. Flow diagram of a mixersettler unit.

2.1.2. Settler balances A non-ideal ow (see Fig. 3) for both phases was used to model the hydrodynamics in this tank (Ingham et al., 2007). The basic model assumes that the solution is split into two streams, one that moves fast (fraction 1 u) and the other that moves slowly (fraction u). The fast moving stream, represented by the upper branch (subindex U) in Fig. 3, is modelled by N perfectly mixed tanks connected in series. Then, in the upper branch, the aqueous phase copper balances are,

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(1-A1) QAm1

VUA1

VUAN

QAUN

Xm1 QAm1,Xm1 A1 QAm1 Xm1

XUN QA1,X1

AL

QAL1
XP1

a1AVL1A

QAL1 xL1A 1AQAL1

a2AVL2A

QAL1 XL2A
1AQAL1

XL1A

XL2A

1AQAL1
XL1B

b1AVL1A

b2AVL2A XL2B

Fig. 3. Hydrodynamic model of aqueous solution in the settler; the hydrodynamic model for the organic solution is the same, but with sub-indexes O instead of A, and copper concentrations Y instead of X.

i1 dX Ui 1 uA Q Am X m X Ui dt V AUi i 2...N dX Ui Q AUi1 X Ui1 X Ui dt V AUi

and the organic phase copper balances are,

 dY L2 Q OL1  a Y L1 k2O Y b 1 k2O Y a L2 L2 dt a2O V OL2 b  dY L2 k2O Q OL1  a Y L2 Y b L2 dt b2O V OL2

a

23 24

10

Therefore, the nal copper concentration at the exit of the settler is a weighted sum of both outlet branches,

X uA X a 1 uA X UN L2 Y uO Y a 1 uO Y UN L2 11

25 26

i1 dY Ui 1 uO Q Om Y m Y Ui dt V OUi i 2...N dY Ui Q OUi1 Y Ui1 Y Ui dt V OUi

In these equations, a stands for active zone, b stands for dead zone and k stands for exchange rate between zones. 2.2. Constitutive equations 2.2.1. Equilibrium The equilibrium isotherm in an extraction unit (see Eq. (7)) is given by (Komulainen et al., 2006),

12

In turn, the slowly moving stream, represented by the lower branch in Fig. 3 (subindex L), is modelled as a plug ow tank in series with two CholetteCloutier units (Aminian et al., 1998). Each of these consists of two perfectly mixed zones, an active (top) and a dead one (bottom). Total and copper balances for both phases in the plug ow tank are,

AX X B

27

Q AL t uA Q Am Ht sAL X P t X m Ht sAL Q OL t uO Q Om Ht sOL Y P t Y m Ht sOL

13 14 15 16

A and B are empirical coefcients tted with process measurements and extractant manufacturer data as follows:

Here, H is the Heaviside step function, which represents a time delay. Copper balances for both phases in the two CholetteCloutier units are given by,

A a ML  b  h i h i  10pH PLS B d Cu2 f Cu2 c PLS BO ML

28 29

 dX L1 Q AL  X P k1A X b 1 k1A X a L1 L1 dt a1A V AL1 b  dX L1 k1A Q AL  a X L1 X b L1 dt b1A V AL1 a  dX L2 Q AL1  a X L1 k2A X b 1 k2A X a L2 L2 dt a2A V AL2 b  dX L2 k2A Q AL1  a X Xb L2 dt b2A V AL2 L2 a  dY L1 Q OL  Y P k1O Y b 1 k1O Y a L1 L1 dt a1O V OL1 b  dY L1 k1O Q OL  a Y Yb L1 dt b1O V OL1 L1
a

17 18 19 20 21 22

where ML is the maximum load (g L1) of Cu in the organic stream (extractant manufacturer data), and pH and [Cu+2] are daily averaged off-line measured values. In these equations, a, b, c, d and f are tting parameters (see Table 1).
Table 1 Isotherm tting parameters. Parameters a b c d f g h m n p Values 0.99 1.02 1.01 35.15 27.15 0.11 444.49 0.10 0.81 8.91

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C.M. Moreno et al. / Minerals Engineering 22 (2009) 13501358 Table 2 Measured variables in LXSXEW copper plant. Measured variables Inputs Aqueous inlet owrate [Cu+2] aqueous inlet Organic inlet owrate [Cu+2] organic inlet Mixer volume Settler volume pH of PLS Free acidity of the lean electrolyte Outputs Volumes of phases in mixer (i = A, O) Flowrates at mixer exit (i = A, O) [Cu+2] in aqueous phase at mixer exit [Cu+2] in organic phase at mixer exit Sampling time (h) 1 1 1 1 1 1 1 1 1 1 1 1 Symbols Qai Xi Qoi Yi Vm Vs pHPLS [H2SO4]LE Vim Qim Xm Ym

Similarly, for the stripping isotherm (see Eq. (8)) (Komulainen et al., 2006),

Y C X D C g ML vol:% Dh p H2 SO4 n LE
m

30 31 32

where vol.% is the % v/v of reactant in the organic and [H2SO4]LE is the free acidity of the lean electrolyte (g L1); g, h, m, n and p are tting parameters (see Table 1). Variables involved in Eqs. (28)(32) were measured from common shift samples in the laboratory by chromatography (see Table 2). Fig. 4a shows daily averages of calculated isotherm parameters A, B, C and D. Further details regarding tting isotherm parameters are given in Appendix A. 2.2.2. Mass transfer In this study, the extraction rate is modelled by a mass transfer expression obtained from the interface theory (Jackson, 1986),

in the laboratory by chromatography from shift samples (see Table 2). Fig. 4b shows daily averages of calculated KE and KS coefcients. 2.2.3. Efciencies Efciencies for both, extraction and stripping units, are dened by,

KE

Q Ai V Am Q K S Oi V Om

X i X m Q X i X m Ai Y Y m V Am eE E Y i Y m Q Oi Y i Y m X X m V Om eS S

33 34

In these equations, the steady state copper concentration gradients (eE Y Y m for an extraction unit and eE X X m for a stripST ST ping unit) are tting parameters (Komulainen et al., 2006). Copper concentrations in Eqs. (33) and (34) (Xi, Yi, Xm, Ym) were measured

gE

eE Y m Y i

Y Yi e X X i gS S m X Xi

35 36

1.2

Scaled values

(a)

0.4

-0.4

-1.2

168

336

504

672

840 A

1008 B

t (h)
1.80

1176 C

1344 D

(b)

K (scaled)

0.80 -0.20 -1.20

168

336

504

672

840

1008

t (h)
0.30 0.00 -0.30 -0.60 0 168 336 504 672 840 1008

1176 E

1344 S

(c)

(scaled)

t (h)

1176 E

1344 S

Fig. 4. Calculated model parameters: (a) Isotherm parameters. (b) Mass transfer coefcients. (c) Efciencies.

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In the mixers, Ym and Xm are the outlet copper concentrations, Yi and Xi are the inlet concentrations, and Y* and X* are the equilibrium concentrations. Fitting parameters, eE1 and eS1, were set by trial and error to minimize the sum of squared errors between simulated and measured outlet copper concentrations. Note that an efciency 1 means that the respective steady state copper concentration gradient is 0; hence, Y Y or X X . Fig. 4c shows daily E S averaged calculated efciencies. In these calculations, copper concentration values averaged every 8 h in the laboratory by chromatography, were used. Nomenclature provides a complete description of the symbols used. Simulations were performed with Simulink software, using calculated model parameters (shown in Fig. 4) updated daily, input variables (shown in Fig. 5) measured hourly, and main model parameters (see Table 3) which were xed during the whole simulation run (56 days). Flowrates and pH were measured on-line

with magnetic owmeters (Siemens MAG 3100) and standard pH-meters, respectively. Copper and acid concentrations were measured in the laboratory by chromatography. In the actual process at Molymet S.A., inlet copper concentration standard deviations ranged between 1 and 2 g L1, owrates between 0.03 and 0.3 m3 h1, and pH varied between 0.8 and 1.8. To keep condentiality, no further process details can be disclosed.

3. Results and discussion First, a parameter sensitivity analysis was carried out to aid model calibration. After calibration, i.e., setting model parameters at xed values, simulations were compared with measured outputs of the actual process, shown in Fig. 6. The same analysis was carried out for both extraction and stripping units.

9.6

(a)

X (scaled)

4.8

0.0

-4.8

168

336

504

672

840

1008

1176
PLS

1344
LE

t (h)
1.4

(b)

Y(scaled)

0.0

-1.4

-2.8

168

336

504

672

840

1008

1176
BO

1344
LO

t (h)
0.08

(c)

QA(scaled)

-0.08

-0.24

-0.40

168

336

504

672

840

1008
PLS

1176

1344
LE

t (h)
0.03

QO(scaled)

(d)

0.01

-0.01

-0.03

168

336

504

672

840

1008
BO

1176
LO

1344

t (h)

Fig. 5. Scaled measured input variables: (a) Copper concentration in aqueous inlet streams. (b) Copper concentration in organic inlet streams. (c) Aqueous inlet owrate. (d) Organic inlet owrate.

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C.M. Moreno et al. / Minerals Engineering 22 (2009) 13501358

Table 3 Model parameters for extraction unit (E) and stripping unit (S). Sub-indexes A and O stand for aqueous and organic phases, respectively. CC stands for CholetteCloutier units. Parameters Fitting parameters Fraction of plug ow in lower branch Steady state concentration gradient Fraction going through lower branch (i = A, O) Fraction in CC units active zones (i = 1, 2; j = A, O) Exchange rate between CC zones (i = A, O; j = 1, 2) Number of upper branch CSTR tanks Calculated from tting parameters (see Appendix A) Upper branch CSTR volume (i = A, O; j = 1, N) Plug ow residence time (i = A, O) Volume of CC units (i = A, O; j = 1, 2) Fraction of dead volume in CC units (i = 1, 2; j = A, O) Symbols f Nominal values (E) 0.3 0.7 0.8 0.6 1.8 2.0 5.3 0.9 14.2 0.4 Nominal values (S) 0.4 1.9 0.9 0.7 1.3 2.0 2.7 1.3 14.3 0.3 Units g L1 m3 h m3

eE
ui aij kij N ViUj

sLi
ViLj bij

2.10

(a)

X (scaled)

1.10

0.10

-0.90 0 168 336 504 672 840 1008 Simulated-E 1176 1344

t (h)
0.85

Measured-E

(b)
Y (scaled)
0.45

0.05

-0.35

168

336

504

672

840

t (h)
2.10

1008 Simulated

1176 1344 Measured

(c)

X (scaled)

1.10

0.10

-0.90

168

336

504

672

840

1008 Simulated-S

1176

1344

t (h)
0.20

Measured-S

(d)

Y (scaled)

-0.20

-0.60

-1.00

168

336

504

672

840

t (h)

1008 Simulated-S

1176

1344 Measured-S

Fig. 6. Simulated vs. measured output variables: (a) Copper concentration in aqueous extraction outlet stream. (b) Copper concentration in organic extraction outlet stream. (c) Copper concentration in aqueous stripping outlet stream. (d) Copper concentration in organic stripping outlet stream.

C.M. Moreno et al. / Minerals Engineering 22 (2009) 13501358

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0.85

Y (scaled)

0.45

0.05

-0.35

168

336

504

672

840

1008
Model

1176
Delay

1344
Real

t (h)

Fig. 7. Comparison between our model and a simplied pure delay settler model. Copper concentration in extraction organic-outlet stream.

3.1. Sensitivity analysis The impact of changing model parameters in the simulation of output variables was assessed. We were particularly interested in detecting high impact parameters that could then be used to t the model to reproduce actual process outputs. Starting from a nominal case, dened by arbitrarily assigned values of input variables and model parameters, the model was simulated several times applying one step change at a time in a given parameter. By trial and error, we found that for both units (extraction and stripping), the split fractions, us, and steady state copper concentration gradients, es, were high impact parameters. Therefore, they were used to calibrate the model for the extraction and the stripping units, running a large number of trial and error simulations. The rest of model parameters, since they did not affect much simulation results, were dened after few simulations. The nal model parameter values are given in Table 3. 3.2. Comparing simulations with measured values Fig. 6 shows simulated model outputs compared with plant copper concentration measurements in both phases. It can be seen that good agreement between simulations and measurements has been achieved for both units. For the extraction unit, relative mean squared errors for the outlet stream copper concentrations were 0.03% for the aqueous phase and 6.76% for the organic phase. In turn, for the stripping unit, relative mean squared errors were 0.07% for the aqueous phase and 2.89% for the organic phase. These differences in the observed errors are probably due to inherent sampling and laboratory measurements variability. For example, measurement errors in the organic phase are larger. In addition, the extraction unit shows much more variability than the stripping unit, which is expected since its feed comes directly from the heap Leaching stage. In turn, this variability is attenuated at the outlet of the stripping unit due to the damping effect of the mixing tanks. Despite this difference, the model is exible enough to reproduce the dynamics of both units well. Furthermore, we compared the performance of our model against a simple delay model (represented as a plug ow) for the settler. The simpler model performs much worse, yielding a relative mean square error of 15.0% for the aqueous phase (not shown) and 44.8% for the organic phase (see Fig. 7). Consequently, it is highly benecial to model the settler with a more complex hydrodynamic model. Fig. 4 also shows interesting features, like the extreme variation of the estimated mass transfer coefcients and efciencies. For instance, the signicant drop in the efciency (see Fig. 4c) of the extraction unit can be attributed to an operational problem and may be useful to identify its cause. Hence, the model can be rened more by associating mass transfer and efciencies with specic operational problems like entrainment, crud formation and variable phase separation times. These would be highly desirable to improve process supervision by alerting process engineers earlier,

so they can take opportune corrective actions. To develop these associations though, exhaustive process operation and data analysis are necessary, after running the model in parallel with the process for long periods. It is worthwhile noting that the model has a prediction horizon of 24 h, since calculated parameters (see Fig. 4) are updated daily based on previous day laboratory data. The model, as it is can be used to implement on-line state and parameter estimations, using for example an Extended Kalman Filter. These estimations can provide further tools to improve process supervision, and even can help to implement automatic control strategies. Furthermore, a dynamic model for the entire extraction SX sub-process can be developed to assess the impact of better operational practices or alternative automatic control strategies on process performance, before implementing them in the real plant, saving time, resources and minimizing the risk of catastrophic events. 4. Conclusions The developed model is a relatively simple form to represent non-ideal ow in mixer settler tanks. We chose this model structure since it represents a good compromise between accuracy and complexity. The main contribution of this work is to show that, with few sensitive tting parameters, the proposed model provides realistic dynamic simulations of industrial mixersettler units. Also, the model can be calibrated with standard measurements and information normally available in current industrial LXSX EW plants; therefore, specic dynamic models for a given industrial SX plant can be developed with moderate effort. Acknowledgements J.R.P. appreciates the support of AGAUR from the Generalitat de Catalunya through Grant 2007PIV-00017 and Ponticia Universidad Catlica de Chile for nancial support for a sabbatical stay at Department DEnginyeria Qumica at Universitat Rovira i Virgili. C.M.M appreciates the support of Molymet S.A. for providing experimental information and Ponticia Universidad Catlica de Chile for granting a PhD scholarship. We appreciate the comments of the anonymous referees that help us to signicantly improve the readability of this paper. Appendix A. Model calibration A.1. Equilibrium isotherm calculations For a collection of pH, and [Cu+2]PLS values, the extractant manufacturer provides several McCabe diagrams, that can be used to obtain isotherm coefcients, A and B, as a correlation of these variables. Additionally, plant measurements of ML, pH, [Cu+2]PLS and [Cu+2]BO (normally available at industrial facilities) were averaged

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daily and, through Eqs. (28) and (29), estimated values of isotherm ^ ^ coefcients A and B were obtained. Then, parameters a, b, c, d and f were tted to minimize the following sum of squared differences,

Min

56 X h i1

^ Ai Ai

i2

^ Bi Bi

i2 

A1

where subindex i refers to the respective day. The tted values are given in Table 1. Similarly, for a collection of [H2SO4] values, a set of McCabe diagrams was given by the manufacturer, yielding a set of values for C and D. Additionally, a set of plant measurements of [H2SO4]LE and vol.% were averaged daily and, through Eqs. (31) and (32), esti^ ^ mated values of isotherm coefcients C and D were obtained. Then, parameters h and p were tted to minimize the following sum of squared differences,

V S 1 u N f uV S sLi Q im 1 f uV S V Lij 2 bij 1 aij V Uij

References

A3 A4 A5 A6

Min

56 X h i1

^ Ci Ci

i2

h i2  ^ Di Di

A2

A.2. Mass transfer and efciency calculations Mass transfer and efciency coefcients were obtained using Eqs. (33)(36). Values of eE and eS were calibrated by trial and error after several simulations. The nal values of eE and eS were those that minimized the mean squared error between the simulated and the measured response. A.3. Calculated parameters in Table 3 They were obtained from,

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