Parameter Sensitivity of Kinetics-Based Hydrometallurgical

Reactor Models
SUSAN A. BALD WIN1and GEORGE P. DEMOPOULO$*

Chemical and Bio-Resource Engineering, Universiry of British Columbia, Vancouver ,BC V6T 124, Canada

Department of Mining and Metallurgical Engineering, McGill University, Montreal, QC H3A 2K6, Canada
In this paper, we have studied the parameter sensitivity of two hydrometallurgical models: REACTSIM (for gold pressure
oxidation) and ZINCSIM (for zinc pressure leaching). The parameters investigated include: the oxygen mass transfer
coefficient, kLa, the activation energy for pyrite oxidation, E,, pyrite and marmatite dissolution stoichiometry, the con-
stant kinetic parameter for ferrous to ferric oxidation and the apparent equilibrium constant for ferric precipitation, KE.
Model predictions were found to be more sensitive to the kinetic parameters under certain conditions than others. For
ferrous to ferric oxidation kinetics, a dramatic model sensitivity was found to the constant kinetic parameter with an
apparent discontinuity at values close to those found in bench scale experiments. The usefulness of simulation programs
was demonstrated when non-intuitive results were obtained showing ZINCSIM sensitivity to sulphate production to
be opposite from what was expected. In the case of KE, solution chemistry was not as sensitive as the heat balance,
which was affected significantly.

Dans cet article, on a etudie la sensibilite des parametres de deux modeles hydrometallurgiques : REACTSIM (pour
I’oxydation sous pression de I’or) et ZINCSIM (pour le lessivage sous pression du zinc). Les parametres etudies incluent :
le coefficient de transfert de matiere de I’oxygene, kLa,I’energie d’activation de I’oxydation de la pyrite, E,, la stoechiometrie
de dissolution de pytie et de marmatite, le parametre cinetique constant pour I’oxydation de l’etat ferreux a ferrique et
la constante d’equilibre apparent pour la precipitation ferrique, KE.On a trouve que les predictions du modele etaient
plus sensibles aux parametres cinetiques dans certaines conditions pratiques que dans d’autres. Pour les cinetiques
d’oxydation de l’etat ferreux a ferrique, on a observe une forte sensibilite du modele au parametre cinetique constant
avec une discontinuite apparente a des valeurs proches de celles trouvees dans des experiences sur banc d’essai. L’utilite
des programmes de simulation a ete demontree lorsque des resultats non intuitifs ont ete obtenus, montrant que la sensibilite
de ZINCSIM a la production de sulfate est a I’oppose de ce qu’on pensait. Dans le cas de KE,la chimiqe de solution n’etait
pas aussi sensible que le bilan de chaleur, qui a ete affect6 de maniere significative.
Keywords: reactor modelling, hydrometallurgy, pressure leaching, pressure oxidation, parameter sensitivity, kinetics.

to which variability in kinetic data influences the predictions

H igh pressure hydrometallurgical reactors for pretreat-
ment of gold ores and concentrates and for leaching of
other materials like zinc concentrates are now widely used
in Canada and the rest of the world (Berezowsky et al,
1991). These are complex 3-phase reactors, which involve
dissolution and precipitation reactions strongly dependent
on the solution chemistry, temperature and vessel pressure.
The success of these hydrometallurgical options for mineral
treatment has prompted researchers to develop mechanistic
models for simulation and optimisation of such processes.
However, the complexity of the interconnected and multi-
phase reactions renders the modelling exercise difficult, and
possibly subject to inaccuracies if any kinetic data input into
the model are not precise.
In this paper we study two simulation packages: (i) gold
pressure oxidation (REACTSIM) (Baldwin et al, 1993), and
(ii) zinc pressure leaching (ZINCSIM) (Baldwin et al, 1995).
These models are unique in that they are based on the intrinsic
kinetics of the reactions as determined in bench-scale labo-
ratory experiments. They can be used to model processes
with variable feed composition, provided appropriate kinetic
data are available for oxidation of each mineral. Other models
have also been developed for zinc pressure oxidation
(Crundwell and Bryson, 1992, Dreisinger and Peters, 1987).
Assumptions made in the various modelling exercises and in
the laboratory experiments vary widely, and the impact of
their variation on the validity of the model predictions is not
known. In t h s study we have attempted to address the extent
‘Author to whom correspondence should be sent. E-mail address:
george@M 1NMET.Lan.McGill.CA
of the REACTSIM and ZINCSIM simulation packages. This
analysis reveals information on the accuracy of applying
these models over a wide range of operating conditions.
Recommendations can be made as to which kinetic parameters
need to be determined more accurately, in order to carry out
improvements to hydrometallurgical reactor models in general.
The two models discussed in this paper were developed at
McGill University by the Hydrometallurgical Group. The
parameters that we have chosen to investigate include (i) the
IMSS transfer coefficient for oxygen, (ii) the activation energy
for mineral oxidation, (iii) the extent of elemental sulphur
produced when pyrite is oxidised in the gold pressure oxida-
tion process, (iv) the constant coefficient kinetic parameter
for ferrous to ferric oxidation, (v) the extent of sulphate pro-
duced when marmatite is leached in the zinc pressure leach
process, and (vi) the apparent equilibrium constant used for
iron precipitation.
First, we present the modelling philosophy followed by a
concise description of the two models. We highlight the rea-
sons for choosing the parameters under investigation and
summarise values reported for them in the literature.
Materials and methods
BACKGROUND
Figure 1 illustrates a typical flow sheet of a gold pressure
oxidation or zinc pressure leach process. The reactor is an
autoclave with multiple stages. This is modelled in REACTSIM
and ZINCSIM as a series of perfectly mixed reactors. The
feed: ore or concentrate, enters the autoclave as a slurry. In

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 76, DECEMBER, 1998 I083
 Aqueous Feed(Hp0
(Au).Elecfrolyie (Zn))
I I
Recycled Solids (Au)
Figure 1 - Flow diagram of a typical gold pressure oxidation or
zinc pressure leach process.
the gold pressure oxidation operation, this may need to be
preheated such that the autoclave operates autogenously.
The required preheat temperature depends on the “fuel”
content of the feed. It was observed that the heat released by
oxidation is proportional to the sulphide and arsenic content
of the feed. Thus, the wt% of sulphide and arsenic in the
feed represent the fuel content. For gold pressure oxidation
the fuel content is varied by adding recycled oxidised solids
as shown in Figure 1. Aqueous feed can be added to any
compartment of the autoclave. In zinc pressure leaching,
acid is required, and is added in the form of recycled electro-
lyte, usually in the first two compartments where most of the
reaction occurs. Oxygen is sparged into each compartment.
These reactors operate under high total pressures (approxi-
mately 30 atm in the case of gold pressure oxidation and 12
atm in the case of zinc pressure leaching), so that the oxygen
solubility is sufficient for the reactions to proceed at effi-
cient rates. The discharge from the autoclave contains: the
metal ion solution, which is sent to the refinery (in the case
of zinc) or for neutralisation (in the case of gold); and reacted
solids, which include un-leached material and precipitates.
The precipitates contain mainly iron, but some gold or zinc
may be lost in form of metals incorporated in the precipitate
crystalline matrix.
The key features of these models and the parameters
under investigation in this study are summarised below.
Reactor model
Reactions in all three phases are modelled, as shown in
Figure 2. Oxygen entering each compartment is trans-
ferred from the gas-phase to the liquid-phase. Opthisation
of oxygen transfer is important since oxygen consumption
and power consumption of the agitators constitute the
major operating costs of the autoclave. CO, is released
due to decomposition of carbonates and needs to be
purged from the vessel. This contributes to lowering of
the oxygen utilisation. Also, steam is lost through the vent
due to evaporation, which contributes to heat losses from
the process. The rate of ferrous to ferric oxidation in the
liquid phase is included in the ZINCSIM model. Ferric
iron concentration needs to be known, so as to calculate
the rate of marmatite leaching and the amount of iron
removed by precipitation. The solid phase comprises min-
erals, which are being leached into solution, precipitates,
and un-leached material. The dissolution processes are
modelled using population mass balance techniques.
Oxygen mass transfer
Oxygen mass transfer rate (OMTR) is determined using
the following equation:
OMTR = -“-(pi2
k a - po2)mol/(L.min) . . . . ,
H tion. Using these parameters to extrapolate kinetic rate
I084 T H E CANADIAN JOURNAL OF CHEMICAL ENGINEERING, V O L U M E 76, DECEMBER. I998
,
Figure 2 - Flow diagram of the inputs and outputs for the mathe-
matical model.
where k,a is the mass transfer coefficient times the spc-
cific surface area of the bubbles, H is Henry’s constant,
P52 is the oxygen partial pressure in the gas phase and
Po2 is the oxygen partial pressure in the liquid phase. The
mass transfer coefficient is specific to each reactor and
therefore is hard to predict. Usually, model simulations
are used to determine this parameter, where k p is calcu-
lated from model predictions that have been compared
with actual plant data. That value is then used in subse-
quent predictions for the same reactor configuration under
different operating conditions. In reality, the value of k, a
could vary depending on the hydrodynamics and possibly
the solids content in the reactor. This would have a large
impact on the performance of the process if it was opcrat-
ing in the mass transfer controlled regime. Because of the
importance of knowing the operating regime of the auto-
clave and the effect of mass transfer on the overall kinet-
ics of the leach reactions, we have investigated the effect
ofkLaon simulation results for a gold pressure leach auto-
clave using BACTSIM.
lntrinsic kinetics
Intrinsic kinetics for each reaction are input into the
model. This includes the parameters of the Arrhenius
expression:
k = A exp(-EJRT) l/min . . . . . . . . . . . . . . , . . . . . . (2)
the pre-exponential factor, A , the activation energy, E,.
and the order of the reaction with respect to oxygen (in the
case of pyrite, pyrrhotite, arsenopyrite, chalcopyrite and
galena, where rate of oxidation = k [ 0 2 ] ” )or ferric ion con-
centration (in the case of marmatite and sphalerite, whcre
the rate of leaching = k[Fe]”). These parameters were
obtained from experimental data published in the literature.
It was observed that kinetic data reported for the same min-
eral, but from different studies, varied somewhat. For
example, in the case of pyrite oxidation, values reported
for the activation energy vary from 46 to 110 klimol,
depending on the temperatures at which the experiments
were performed. Some of these data were obtained at tem-
peratures lower than those encountered in pressure oxida-
 constants at the appropriate temperatures of both pressure
oxidation and leaching can lead to enormous inaccuracies.
One study of pyrite oxidation, in the temperature range
140 to 180"C, found two distinct straight lines on the
Arrhenius ln(k) versus 1/T plot (Papangelakis and
Demopoulos, 1991). The activation energy found between
140 and 160°Cwas 46.2 kJ /mol and between I60 and 180°C
was found to be more than twice as high at 110.5 kJ/mol.
Because the modelled gold pressure oxidation processes
operate at high temperatures (190 to 25OoC), the kinetic
equation with higher activation energy for pyrite oxida-
tion was used in REACTSZM. Still, since only three data
points were used to determine this parameter from the
Arrhenius plot, a large uncertainty can be expected. From
the scatter of points on the plot we deemed the activation
energy to be accurate to within f 10 kJ/mol. Later, we pre-
sent the sensitivity of model predictions to this magnitude
of parameter uncertainty.
Ferrous to ferric oxidation
The rate of ferrous ion to ferric ion oxidation has been
modelled in the literature as a second order reaction with
respect to ferrous ion concentration and first order with
respect to dissolved oxygen partial pressure:
d Fe2'
dt
= k2 [Fe2+]?Pol mol/(L. min) . . . . . . . . . (3)
where,
k,- = A exp(-80.3/RT) L/(mol.min.atm) . . . . . . . . . . (4)
Reported values for the rate constant, k,, are variable and
highly dependent on the solution chemistry. A study by
Dreisinger and Peters (1989) examined ferrous to ferric
ion oxidation rates in solutions with various zinc sulphate
and sulphuric acid concentrations. Values for the rate con-
stants derived from their data varied by 40% even after
accounting for the sulphuric acid and total sulphate con-
centrations. In another study of ferrous to ferric ion oxi-
dation, Baldwin and Van Weert (1996) found k2 to be
0.0 192 L/(mol.min.atm) in a solution with initial concen-
trations: 1.O M H,SO, and 0.1 M FeSO,. For the ZZNCSZM
model, an empirical expression obtained fiom the Dreisinger
and Peters (1989) data is used for the pre-exponential factor:
A = l o x 109(1.0+5.0[cu2+]o~s)
.. ...
[SO~-]'[H2S04]-o'5(L.mol)'~5/(min-atm).
where, [SO:-]' is the total sulphate concentration exclud-
ing sulphuric acid. In our model, we have assumed that
the orders with respect to Cu, SO, and H2S04 in this cor-
relation are accurate, and we have investigated the sensi-
tivity of ZINCSIM predictions to the constant coefficient
of Equation 5 in the range 5.0 to 14.0 x lo9 (L.mol)'.S/
(mimatm). This wide range of values was chosen because
of the aforementioned40% variability in the Dreisinger data.
In ZINCSIM , the ferrous and ferric ion concentrations in
the aqueous phase in the autoclave are calculated by
including material balance equations for ferrous and ferric
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 76, DECEMBER, I998
ions in the model. In the ferrous ion material balance
equation, ferrous ions are generated from dissolution of
iron containing minerals and are consumed by oxidation
to ferric ions. In the ferric ion material balance, ferric ion5
are produced from oxidized ferrous ions and are removed
by precipitation as jarosite (Baldwin et al, 1995).
Stoichiometry
The mass balance equations in each simulation package
are based on the stoichiometry for every reaction. Since
the zinc pressure leach process was developed so as to
avoid sulphate production, most sulphides are oxidised to
elemental sulphur at the temperatures encountered there
(140 to 150°C). One exception is pyrite oxidation, which
produces sulphate. In the gold pressure oxidation process,
where higher temperatures are reached (200 to 250°C). all
the sulphide minerals are assumed to oxidise to sulphate.
However these assumptions are not absolutely accurate
for both processes. In zinc pressure leaching, it has been
found that up to 5% of the non-pyritic sulphur could be
oxidised to sulphate (Chalkley, 1993). The stoichiometric
equations for sphalerite oxidation to elemental sulphur
and sulphate are given below:
ZnS + Fe2(S0,)3 -+ZnSO, + 2FeSO, + So . . . . . . . (6)
S + 3/2 0, + H,O + SO$-+ 2H+ . . . . . . . . . . . . . . (7 1
We can see that the amount of sulphur oxidation changes
the moles of oxygen consumed and sulphate produced.
The rate of mineral leaching depends on the oxygen pre-
sent in solution and the rate ferrous to ferric ion oxidation
and iron precipitation depend on sulphuric acid concen-
tration. Thus, assumptions on the extent of sulphide con-
version to sulphate are expected to impact on the model
predictions. In addition, the heats of reaction differ
markedly. For ZnS conversion to sulphate, A H::: =
-818.6 kJ/mol, which is almost 30 times greater when
compared with A H::, = -29.6 kJ/mol for ZnS conversion
to elemental sulphur only. Thus, even if only 5% of ZnS
is converted to sulphate, this may influence the energy
balance and the predicted operating temperature. Results
for ZZNCSIM simulations performed with various amounts
of sulphate produced from 0 to 5% will be presented later.
Gold pressure oxidation simulations using REACTSIM at
higher temperatures assume pyrite and arsenopyrite oxidise
all the way to sulphate. However, studies in the literature
have indicated that anywhere between 0 to 30% of oxi-
dised pyrite forms elemental sulphur (10% in McKay and
Halpern, 1958; 7% in Gerlach et a]., 1966, and 25% in
Bailey and Peters 1976). The stoichiometric equations for
sulphate production and elemental sulphur production,
respectively, are given below:
2FeS, + 7 0 , + 2H20+ 2FeS04+ 2H2S0, . . . . . . . . ( 8 )
2FeS2 + 40, -+ 2FeSO, + 2S0 . . . . . . . . . . . . . . . . (9)
Also, as expected, the heat of reaction for these two reac-
tions are quite different: AH:, = -2,600 kJ/mol for
Equation (8) and AH::, = -826.5 kJ/mol for Equation (9).
Results for REACTSIM simulations performed with various
amounts of pyrite (between 0 to 30%) oxidised to ele-
mental sulphur will be presented later.
I085
 TABLE1 TABLE 2
Standard Reactor and Feed Settings for REACTSIM Simulations Standard Reactor and Feed Settings for ZlNCSlM Simulations
Parameter Value Parameter Value
Number of Compartments 5 Number of compartments 4
Volume of Compartment # I 8.7 m3 Volume of compartment 1 22.4 m3
Volume of Compartments #2, 3 , 4 and 5 4.3 m3 each Volume of compartment 2 17.4 m3
Total Reactor Pressure I7 atm Volume of compartment 3 17.2 m3
Temperature 1 90°C Volume of compartment 4 17.4 m3
Total Presssure 12.5 atm
Mineralogical Composition
Pyrite 66.5 %wt Mineralogical Composition
Arsenopyrite 26.0 %wt Marmatite (8.9% Fe) 60.5 wt%
Flow rate of Feed Solids 2.3 tonh Marmatite (3.5% Fe) 23.9 wt%
Feed Slurry Density 73 %wt solids Pyrite 1.08 wt%
Pyrrhotite 2.65 wt%
Galena 6.36 wt%
Apparent solubility product for iron precipitation Marcasite 1.08 wt%
Flow rate of feed solids 270 kglmin
In zinc pressure leaching, iron is leached into solution Feed slurry density 70.0 %
from marmatite, pyrite, pyrrhotite and any other iron minerals Feed slurry temperature 15°C
in the concentrate. Iron precipitates from solution in various
forms: jarosite; goethite or hematite, depending on tempera- Aqueous Feed Streams
To Compartment 1 To Compartment 2
ture, and the iron and acid concentrations. Much qualitative
information exists in the literature on the nature of iron pre- Flow rate 1380 L/min 500.0 L/min
cipitates in zinc pressure leaching. For the Cominco zinc Temperature 60°C 30°C
pressure leach conditions (140°C 12 atm, 30 g/L acid) iron Zn2+ 50.0 g/L 50.0 g/L
Acid 161.0 g/L 161.0 g/L
was found to precipitate as jarosite. Lead, leached from
galena in the concentrate, forms insoluble lead sulphate that
combines with ferric ion in solution to form lead jarosite:

0.5PbS04 + l.5Fe2(S04)3+ 6H20

cNI

i=l
Mj(Hi - I f o ) = c
NR

-+ Pb,,, Fe3(S04), (OH), + 3H2S0, . . . . . . . . . (10)
Otherwise, ferric ion precipitates as hydronium jarosite:
1.5Fe2(S04)3+ 7H20 -+ (H30)Fe3(S04)2(0H)6
+2.5H2 SO, . . . . . . . . . . . . . . . . . . . . . . . . . . .
However, little thermodynamic, or other quantitative
data, have been reported that could be used to predict the
type and amount of precipitate formed under certain condi-
tions. Femc ion and sulphuric acid concentrations from the
exit of several zinc pressure leach operations were surveyed
during the ZINCSIM development (Baldwin et al, 1995).
From these values, an apparent equilibrium constant, KE,
was used as an approximation for the solubility product for
Reactions 10 and 1 1 :
KE = [Fe3+]/[H2S04]moVmol . . . . . . . . . . . . . . . . (12)
A value of KE = 0.219 moVmol was chosen for the stan-
dard ZINCSIM simulations of the Cominco pressure leach.
Since this value is based on plant data rather than controlled
laboratory experiments, it may not be applied suitably to
processes other than the Cominco operation. In this study,
we have investigated how the range of uncertainty in this
parameter impacts on model predictions. Values for KE from
0.150 to 0.300 mol/mol were used in model predictions.
The heat balance
The simulation programs, REACTSIM and ZINCSIM,
perform a heat balance for each compartment of the auto-
clave so as to calculate the stable, steady state operating
temperature for that compartment. The heat balance equa-
tion used is given below:
j=l
(J/min) . . . . . . . . ( 1 3 )
AHrXn,yj
where, NI is the number of feed streams coming into the
compartment, which would typically include the slurry from
the previous compartment or fresh feed and any aqueous
feeds. Miis the molar flow rate of feed stream i in mournin,
(11) Hi is the enthalpy of the incoming feed stream in J/mol and
H, is the enthalpy of the slurrj exiting the compartment in
J/mol. The term on the left hand side of Equation (13) rep-
resents the heat removed. The term on the right hand side of
Equation (1 3 ) represents the heat generated. NR is the num-
ber of reactions occurring in the compartment. AHrxnjis the
heat of reaction in J/mol for reactionj at the steady state
temperature of the compartment and E~ is the extent of reac-
tionj in moumin.
Equation (13 ) has been cast in the form Heat Removed =
Heat Generated since the classic Van Heerden Diagram
approach is used to find the steady state temperature (Van
Heerden, 1952). In this method, the material balance equa-
tions are solved for fixed temperatures over the temperature
range of interest. The Heat Removed and Heat Generated
values are plotted on the same set of axes versus tempera-
ture, as can be seen later in Figures 10 and 14. A steady state
temperature is found at the intersection of the two lines.
That is where Heat Removed equals Heat Generated.
Unstable steady states occur where the slope of the Heat
Generated curve is greater than the slope of the Heat
Removed line at the intersection. Otherwise, the steady state
is assumed to be stable.
MODELSIMULATIONS
To examine the parameter sensitivities, model simula-
tions with different parameter values over their range of
uncertainty were compared with standard simulations.
Standard model input parameters for REACTSIM are given

I086 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 7 6 , DECEMBER, 1998

 TABLE3
Standard Values for Parameters and the Range of their Values
used in the Sensitivity Studies
Parameter Standard Value Range
REACTSIM
1. Oxygen mass transfer coefficient 35 5-50
(1 /min), k,a
2. % Reacted pyrite converted to 0 0-30
elemental sulphur
3. Pyrite oxidation activation energy 110 100- 120
(kJ/mol), E,
ZINCSIM
4. Ferrous to ferric oxidation constant 10 5-14
coefficient kinetic parameter
(x I 09 (L.moI)'.s/(min.atm))
5. % Reacted marmatite converted to 0 0-5
sulphate
6. Iron precipitation equilibrium 0.129 0.15-0.30
constant (mol/mol),K E
in Table 1. The Cominco zinc pressure leach conditions
(McKay, 1994) were chosen as the standard conditions for
ZINCSZM simulations and are presented in Table 2. The
parameters investigated and their range of values are pre-
sented in Table 3.
Results and discussion
GOLDPRESSURE OXIDATION MODELLING WITH REACTSIM
Oxygen mass transfer coeflcient, kLa
It was expected that the model sensitivity to this parameter
would depend on the regime (mass transfer controlled or
reaction rate controlled) that the autoclave was operating in.
Figure 3 presents the calculated feed preheat temperature
required for operation of the autoclave at 190°C versus the
fuel content of the feed for different values of parameter kLa.
The fuel content of the feed refers to the total sulphur and
arsenic content of the feed concentrate or ore. We use the
term fuel content since it was noticed that the heat released
from oxidation of the sulphide minerals studied (pyrite,
arsenopyrite and pyrrhotite) was roughly proportional to
their combined sulphur and arsenic content. It is most desir-
able to operate the autoclave autogenously, that is without
any preheat of the feed. For example, if the concentrate or
ore contains 4.5 S+As wt%, then from Figure 3, assuming
kLa = 35 l/min (the open circles), the feed temperature
should be 40°C for autogenous operation at 190°C. If the
fuel content of the feed is lower than 4.5 S+As wt% then the
feed must be preheated to higher temperatures. If the fuel
content is higher than 4.5 S+As wt% then cooling may be
required to prevent the autoclave temperature from exceed-
ing 190°C. In Figure 3, four curves are presented for four
different kLa values, 10, 20, 35 and 50 l/min, respectively.
The operating line for kLa =lo l/min is very far away from
the other lines and gives very different calculations for the
feed preheat temperature versus fuel content required for
autogenous operation at 190°C. For higher values of kLu (35
to 50 l/min) the curves are closer together and the model
predictions do not appear to be as sensitive to uncertainties
in the value of kLu (35 to 50 l/min). This could be because
at these high kLa values the reactions are not mass transfer
controlled. However, for lower kLa values, where the reac-
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 76, DECEMBER, 1998
60
50 I I I I
3 4 .5 b I H 0
Fuel Content of the Fccd (S + As wt%)
Figure 3 - REACTSIM predicted feed pre-heat temperature ("C)
required for operation at 190°C versus the fuel content (S + As
wt%) of the feed at four different assumed k,a values: 10 (open
square), 20 (filled square), 35 (open circle) and 50 (filled circle)
l/min.
Y.5a , I
Figure 4 -REACTSIM predicted fuel content (S + As wt%) of the
autoclave feed required for autogenous operation at 190°C (open
square), overall sulphide conversion (filled square) and autoclave
residence time (min) (open circle) versus assumed values for k,a
( I /min).
tions are mass transfer controlled small variations in the
value of kLa give large differences in the model predictions.
To look more closely at the effect of the kLa parameter
value on model predictions, we calculated the fuel content
of the feed required for autogenous operation of the auto-
clave at 190°C when the feed temperature was 30°C. This is
presented versus kLa in Figure 4 (open squares). The figure
shows that the calculated fuel content required for autoge-
nous operation at 190°C is very sensitive to kLa parameter
values at low kLa and not so sensitive at high kLa values. The
calculated fuel content decreases with kLa since at higher kl,u
values the reactions are not mass transfer controlled and
proceed more rapidly thus releasing more heat. Under these
conditions the feed should have a lower fuel content so that
the temperature does not exceed 190°C in the autoclave. In
the model, we vary the fuel content of the feed by adding
recycled oxidised solids to a fixed amount of concentrate.
The disadvantage of adding recycled oxidised solids is that
the residence time of the autoclave goes down. This can
been seen in Figure 4. The Figure shows the residence time
increasing sharply at the lower mass transfer coefficients.
The longer residence time might be expected to yield hgher
sulphide conversions. However, the mass transfer limited
kinetics under these conditions are too slow and conversion,
despite increased residence time, drops steeply at low k,u.
I087
 Standard E. / A
Low Temperature E , / A
120 Standard E./A - 10 kJ
' I I -7
20
0 5 10 15
Fuel Content of the Feed (S
20
+ As wt%)
25
Figure 5 - REACTSIM predicted feed pre-heat temperature ("C)
required for operation at 190OC as a function of fuel content in the
feed (S + A s wt%) using different values for the pyrite oxidation
activation energy (kJ/mol). E, and A obtained from high tempera-
ture studies are referred to as the standard values. For this case, E,
was varied *I0 kJ/mol. The parameters from the low temperature
study were also used in the simulation to illustrate the vastly dif-
ferent results obtained when kinetics are extrapolated far from the
range of conditions in which they were obtained.
In summary, from Figure 4 the model is very sensitive to
k,a values in the mass transfer controlled regime, whlch for
the particular autoclave simulated here is where kLa < 35
limin. When the reactions are not mass transfer controlled,
accurate estimates for kLa are not necessary since the model
predictions are relatively insensitive to kLuunder those condi-
tions. Thus, in order to use the model successfully, the user at
least should know in which regime the autoclave is operating.
Pyrite oxidation kinetic parameters
For REACTSZM simulations, the high temperature (160 to
180°C) Arrhenius expression from Papangelakis (1 991) was
chosen as the most appropriate, since the autoclave operates
autogenously at 190°C. This is referred to as the standard
case in Figure 5. The activation energy here is varied in the
range f 10 kJ/mol. Additional simulations were performed
using the low temperature activation energy, 46 kJ/mol. In
Figure 5, feed preheat temperature for autogenous operation
is plotted versus fuel content. With such high activation
energies (by high we refer to the absolute value): 100 (open
circle), 110 (open square) and 120 kJ /mol (closed circle),
the feed preheat temperature lines are still quite steep, show-
ing that the dependence of the rate constant on temperature
is quite dramatic. For example, if the fuel content of the feed
to the autoclave drops by I%, the feed preheat temperature
has to be increased by 5OoC. Contrast this to the results
using the low temperature Arrhenius parameters (closed
square) where the activation energy is less than half. There,
a 1% change in fuel content necessitates a 15°C adjustment
in preheat temperature to maintain the operating tempera-
ture at 190°C.
Because the activation energy is in the exponent, small
changes in its value impact greatly on the value of the rate
constant for pyrite oxidation. In Figure 6, we have plotted
the overall sulphide conversion and the fuel content of the
feed required for autogenous operation at 190°C when the
feed temperature is 30°C versus activation energy. In these
simulations, the standard, that is the ones determined at
higher temperatures, Arrhenius parameters were used.
Figure 6 shows the effect of variation in the activation energy
*lo kJ/mol on the model predictions for sulphide conversion
I088 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 76, DECEMBER, 1998
-1
Fuel Cbntent 0
Sulphide Conversion
-0.9 2
.-m
t
-0.8 20
'd
-0.7 3
3'
100 105 110 115
Activation Energy, E, (kJ mol-')
,1g5
Figure 6 -REACTSIM predictions for fuel content (S + A s wt%)
required for autogenous operation at 190°C and total sulphide con-
version as a function of the different assumed activation energies
in kJ/mol for pyrite oxidation.
and fuel content for autogenous operation. If the activation
energy is 100 kJ/mol then the model calculates sulphide
conversion to be 68%. However, if the activation energy
were 120 kJ/mol then the model would predict sulphide con-
version to be nearly loo%! Thus, *lo kJ/mol uncertainty in
the value for the activation energy results is very different
model predictions. This is due to the highly non-linear rela-
tionship between the reaction rate and activation energy.
The predicted fuel contents required for autogenous opera-
tion are also quite different over the range of uncertainty for
the activation energy, as seen in Figure 6 .
These results show that the model predictions are very
sensitive to variations in the value for pyrite oxidation kinetic
parameters. The model is so sensitive to these parameters,
especially the activation energy, that a more systematic
approach should be taken in carrying out experiments for
the determination of temperature dependence of rate con-
stants. More than three data points are needed. Duplicate
experiments should be performed to obtain error bars.
Parameters should not be used to extrapolate for rate con-
stants outside of the temperature range in which the data
were collected.
Percent pyrite oxidised to elemental sulphur
Simulation results for autogenous operation and total sul-
phide conversion are shown in Figures 7 and 8. Surprisingly,
the model predictions were largely unaffected by the
amount of elemental sulphur produced despite the large dif-
ferences in heats of reaction. This is true for the range 0 to
30% pyrite converted to Sopresented here. Also, predicted
overall sulphide conversions are affected only marginally.
As mentioned previously, the assumed stoichiometry also
affects the mass balance, particularly the acid concentration.
This is not evident in the refractory gold pressure oxidation
simulations since changes in solution chemistry are not
modelled in REACTSIM. The effect of stoichiometry on
solution chemistry will be discussed in a later section on
zinc pressure leaching, where iron and acid concentrations
are important.
ZINC PRESSURE LEACH MODELLING WITH ZINCSIM
Rate of ferrous to ferric ion oxidation
It is well known in zinc pressure leaching that a zinc con-
centrate with low iron content will not leach. Oxidation of
sphalerite and marmatite by dissolved oxygen is too slow.
 '5 .
\\\
I - -
?"A ;: 3:.5 ; 115
Fuel Content of the Feed (S
; 515
+ As wt%)
Figure 7 - REACTSlM predicted feed pre-heat temperature ("C)
for operation at 190°C as a function of fuel-contentof the feed (S +
As wt%) assuming no reacted pyrite is converted to elemental sul-
phur only (open square), assuming 15% of the reacted pyrite con-
verts to elemental sulphur only (tilled square) and assuming 30% of
the reacted pyrite converts to elemental sulphur only (open circle).
.-8
m 32
2 0.995
0.98 I I I I , I
0 5 10 15 '0 25 30
L/a I;& convertcd to So
Figure 8 -REACTSIM predicted total sulphide conversion using
the fuel content (S + As wt%) required for autogenous operation at
190°C versus the assumed amounts of reacted pyrite converted to
elemental sulphur only.
But, with adequate ferric ion as oxidising agent, zinc leach-
ing takes place at temperatures below 160°C. A positive
feedback loop exists in the reactions involved in the process.
Sphalerite or marmatite reacts with ferric ion to produce
zinc in solution and ferrous ion. The ferrous ion is then oxi-
dised back to ferric ion by dissolved oxygen:
ZnS + Fe,(SO,),+ ZnSO, + 2FeS0, + So . . . . . . (14)
2FeS04 + f0, + H,SO, + Fe,(S0,)3 + H,O . . . . (1 5)
Thus, the ferrous ion product from the first reaction is
recycled back to ferric ion in the second reaction. Efficient
leaching of sphalerite and marmatite continues as long as
ferric ion is not removed from solution by precipitation.
Thus, the rate of sphalerite and marmatite leaching depends
also on reaction 15, the rate of ferrous to ferric ion oxida-
tion. Sensitivity of model predictions to the constant value
in the rate expression for ferrous to ferric ion oxidation can
be seen in Figure 9. Here, we have plotted the ferrous and
ferric ion concentrations predicted by the model for the first
compartment of the autoclave versus several different val-
ues used for the constant coefficient in Equation 5. From the
graph, it can be seen that values of this coefficient less than
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 76, DECEMBER, 1998
* -.J
0 i
S 9 10
I
I1 12 I :I
I
11
Ferrous to Ferric Oxidation Kinctics (:oristarit ( x IO..')
Figure 9 - ZlNCSIM predicted ferrous (open squares) and ferric
ion (closed squares) concentrations (g/L) in the first compartment
versus different assumed values for the constant coefficient para-
meter ((L.m~l)'.~/(min.atm)) in the kinetic equation for ferrous to
ferric oxidation kinetics under zinc pressure leach conditions.
30
'5
(0, 1, 2, 3, 1 a n d 5
26
I
135 140 145 150 1.55 1 fiO
Tmipwatiire ( " ( ' )
Figure 10 - Z/NCSIM heat balances for the first Compartment
conducted for different assumed extents of marmatite conversion
all the way to sulphate. The dashed line represents the heat
removed (GJ/mol) and the solid lines represent the heat generated
(GJ/mol). Increasing line thickness corresponds to increasing per-
cent sulphate from 0 to 5% in increments of 1 %. The circles mark
the stable steady state solutions.
9.5 x lo9 yielded extremely small concentrations of ferric
iron. Under these conditions, the model predicts little or no
marmatite leaching. There is a critical value for this constant
parameter where the ferric ion concentration suddenly
increases. The reason for this must be that marmatite leach-
ing suddenly takes off, increasing the total iron in solution
and, through the feedback loop (reaction 15), the ferric ion
concentration, which then further increases the marmatite
leaching. The ferrous and ferric ion concentrations remain
somewhat constant for coefficients greater than 9.5 x lo9.
This is due to the precipitation of ferric ions and the assumed
apparent equilibrium. In this case, the model appears to sug-
gest that this value could be a bifurcation point of some sort
comparable to ignitiodextinction phenomena seen in other
positive feedback systems. The standard value averaged
from the Dreisinger and Peters (1989) data is very close to
this point. Some of the measured ferrous to ferric ion oxida-
tion rates reported in Dreisinger and Peters (1989), if used in
the model, would result in predictions of very low marmatite
conversions under the conditions investigated. Perhaps the
I OX9

Percent Marmatite Oxidisrd to Sulphatr
Figure 1 1 -ZlNCSlM predicted steady state temperature ("C) for
the first compartment as a function of percent oxidation of mar-
matite all the way to sulphate.
catalysing effects taking place in the zinc pressure leach
process to accelerate ferrous to femc ion oxidation are not
seen or well characterised in bench-scale experiments.
These kinetics deserve more complete investigation.
Fraction of leached marmatite oxidised to sulphate
Figure 10 shows the method by which ZINCSIM deter-
mines the energy balance for the zinc pressure leach auto-
clave simulation. The solid lines represent the heat generated
due to the reactions taking place in the autoclave. Six dif-
ferent lines are presented corresponding to different model
simulations run with different assumptions for the percent of
marmatite oxidised to sulphate. The values used for the per-
cent of marmatite oxidised to sulphate increase with line thick-
ness, and equal 0, 1,2,3,4 and 5 respectively. It can be seen
in the Figure that the amount of heat generated increases
with greater amounts of marmatite converted to sulphate, as
was expected. The dashed line represents the heat removed.
This line does not depend on the amount of marmatite con-
verted to sulphate and remained the same for all six simula-
tions. The stable operating temperature for each simulation
can be found at the intersection of the solid lines and the
dashed line. There are two intersections between each solid
line and the dashed line, the first intersection is not a stable
solution, as determined by the criteria of Van Heerden (Van
Heerden, 1952). The second intersection, as indicted by the
open circles in Figure 10, is a stable solution and the oper-
ating temperature is determined at this point. The closeness
of the stable solution to the unstable solution implies that
reaction extinction may occur, should fluctuations in input
conditions cause the steady state temperature to drop. This
has not been seen in actual zinc pressure leach operations.
However, this multiple steady state phenomenon is typical
for an exothermic reaction in a continuous stirred tank reactor,
and is not a surprising result.
Figure 10 shows that the heat balance is quite sensitive to
the assumed amount of sulphate produced in marmatite oxi-
dation. The degree of uncertainty is only 0 to 5% marmatite
converted to sulphate, but the predicted steady state temper-
atures at 0 and 5%, respectively, differ by 17OC. The effect
is non linear, as shown in Figure 11. Considering only the
effect of sulphate production on the heat of reaction, one
would expect a linear increase in heat generated, which
appears to be so in Figure 10, excluding the line for 5% con-
1090 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 76, DECEMBEK, 1998
Prrccnt. Marnlatite Oxidisrd to Sulphatr
Figure 12 - ZfNCSlh4 predicted marmatite conversion (open
square), acid (closed square), ferrous ion (open circle) and ferric
ion (closed circle) concentrations (g/L) in the first compartment
versus assumed amounts (in %) of reacted marmatite converted all
the way to sulphate.
version to sulphate. However, there is not a linear relation-
ship between predicted steady state temperature and percent
marmatite oxidised to sulphate. This is due to the highly
non-linear nature of the heat balance equation, the extents of
reaction in Equation (13) being dependant on temperature,
and the coupling of the heat balance to the material balancc
equations. In addition, because the steady state temperature
increases with percent marmatite oxidised to sulphate, onc
would expect the extent of marmatite conversion to increase
also. But this was not the case, as can be seen in Figure 12
(open squares), where the marmatite conversion drops from
0.75 to 0.695. Increased sulphate production results in
increased acid concentrations, as can be seen in Fig. 12
(solid squares). Acid concentration has an inverse effect on
ferrous to ferric ion oxidation kinetics (see Equation 5).
Thus, the ferric ion concentrations are lower with increased
percent marmatite oxidation tu sulphate (closed circles in
Figure 12). Thus, the extent of marmatite oxidation, which
is proportional to ferric ion concentration, is less. This effect
of increased sulphate production counteracts the increased
heat of reaction with greater percent conversion of mar-
matite to sulphate. This particular parameter sensitivity
study is an excellent illustration of the difficulty of intu-
itively anticipating the effect of certain parameters on sys-
tem performance, due to the complex interrelationship of all
events. At first consideration, one would have expected
more sulphate production, which gives off more heat and
raises the steady state temperature to result in increased
marmatite conversion. However, the activation energy for
marmatite leaching is quite low (E, = 37.4 kJ/mol) and the
effect of temperature would not be great. But, as the simulation
results show in Figure 12, the conversion of marmatite actu-
ally decreases with sulphate production, counter-intuitively.
The negative effect of increasing acid concentrations
counter-balances the heating effect. The actual compounded
effect can only be predicted by doing the calculations and
cannot be arrived at intuitively. This is one of the benefits of
simulation programs as tools to predict the effects of oper-
ating parameters on process performance, but, also, can be a
pitfall in assessing the accuracy of the model.
Apparent equilibrium constant for iron precipitation
The most obvious effect of this parameter to be expected
would be on the ferric ion and sulphuric acid concentrations.
This is shown in Figure 13. With increasing KE, acid con-

I1 I
0.14 0.16 0.1s 0.2 0.22 0.24 0.26 0.28
10.73
0..1
5
IiE (mol/~nol)
Figure 13 - ZlNCSlM predicted marmatite conversion (open
square), acid (closed square), ferrous ion (open circle) and ferric
ion (closed circle) concentrations (g/L) in the first compartment
versus assumed apparent equilibrium constants (KE, mol/mol) for
iron precipitation.
centration drops and ferric concentration increases, as
expected, although the effect is not dramatic over the para-
meter range investigated. Ferric ion concentration only
increases from 2 to 3 g/L and the marmatite conversion
increases only a few percent (Figure 13). These results indi-
cate that the model is not very sensitive to KE values over
the range investigated. However, even with a few percent
increase in conversion, the heat balance for the first com-
partment of the autoclave changes significantly. This is
shown in Figure 14, where the heat generated (solid lines)
and the heat removed (dashed line) are plotted versus tem-
perature for six different KE values. In the Figure, the stable
steady states are indicated by the dots. Note that for the two
lowest values of KE: 0.150 and 0.180 (the bottom two thin-
ner lines), there is no stable steady state solution. The two
lines representing heat generated (solid line) and heat
removed (dashed line) do not intersect. It was observed pre-
viously, that the two steady state solutions of the heat bal-
ance, the lower unstable and the upper stable, were very
close to one another. This implied that with fluctuations in
the process, the reactions in the autoclave could extinguish.
This is what happens when lower values are assumed for the
apparent equilibrium constant. Here, the parameter sensitivity
study illustrates a situation where, on the one hand, varia-
tions in the parameter over its range of uncertainty do not
result in significant changes for the model predictions of
solution chemistry. Whereas, on the other hand, non linearities
in the mass and energy balance equations result in very differ-
ent predictions for the stable steady state temperature. Thus,
this parameter value still needs to be determined acurately.
Conclusions
In this study, we have investigated the sensitivity of two
complex hydrometallurgical reactor models to the following
parameters: For REACTSIM: mass transfer coefficient, kLa,
pyrite dissolution activation energy, E,, percent pyrite con-
version to So, for ZINCSIM: the constant kinetic parameter
for ferrous to ferric oxidation, percent conversion of marmatite
to sulphate and the apparent equilibrium constant for iron
precipitation, KE. Our results have shown that such models
are very sensitive to some kinetic parameters: k[,a in the
mass transfer controlled regime and the activation energy, En,
especially since it is in the exponent of the rate expression.
TFfE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 76, DECEMBER, 1998
IIeat <;eric~aic~I , A
(0.15, n.is. o.21
0.24. 0.27 antl 0.:10 rriol/inol
Figure 14 - ZINCSIM heat balances for the first compartment
conducted for different assumed apparent equilibrium constants
(KE,mol/mol) for iron precipitation. The dashed line represents the
heat removed (GJ/mol) and the solid lines represent the heat gen-
erated (GJ/mol). The dots mark the stable steady state solutions.
An apparent discontinuity was observed in the dependence
on the constant coefficient in the rate expression for ferrous
to ferric ion oxidation. We believe that the feedback loop in
marmatite leachmg with simultaneous ferrous to ferric ion
oxidation contributes to this phenomenon. This result is sig-
nificant since the constant coefficient parameter obtained
from averaged kinetic data from laboratory experiments
reported in the literature is very close to the discontinuity.
This exercise also showed that models can be a powerful
tool for predicting the effect of certain parameters where
their effect is not intuitively induced. This was seen where
the effect of percent maramtite reacted to sulphate effected
the marmatite conversion in the opposite way to what was
expected. This was due to complex relationships between
reaction rates and solution chemistry. Another surprising
result was that the model predicted steady state temperature
was very sensitive to the apparent equilibrium constant for
ferric ion precipitation, KE, while the predicted solution
chemistry was not. In short, this study leads to two recom-
mendations: the necessity for accurate kinetic parameters
determined over the range of interest to be used in the
model, and the usefulness of the modelling exercise in deter-
mining the effect of process parameters.
Nomenclature
A = ferrous to ferric ion oxidation kinetics pre-exponential
factor, (L.mol)l S/(min.atm)
E, = activation energy, (J/mol)
= extent of reaction j, (mol/min)
2 = Henry's constant, (atm/(L.mol)
Hi = enthalpy of incoming stream, (J/mol)
H, = enthalpy of outgoing stream, (Jlmol)
AHm,,= heat of reaction, (J/mol)
AfY,?z: = heat of reaction at 298K, (J/mol)
k = rate constant, (I/min)
k, = second order rate constant for ferrous oxidation,
(L/(mol.min.Pa)
KE = apparent equilibrium constant for ferric precipitation,
(mol/mol)
k,a = oxygen mass transfer coefficient, ( I /min)
M = molar flow rate, (mol/min)
OMTR = oxygen mass transfer coefficient, (mol/(L.min))
PlO2 = partial pressure of oxygen in the gas phase, (atm)
3 = partial pressure of oxygen in the liquid phase, (atm)
= gas constant, (J/(mol.K))
1091
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