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2005-HeapSim - Unravelling The Mathematics of Heap Bioleaching - pdf-1
2005-HeapSim - Unravelling The Mathematics of Heap Bioleaching - pdf-1
2005-HeapSim - Unravelling The Mathematics of Heap Bioleaching - pdf-1
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David G. Dixon
Department of Materials Engineering
University of British Columbia
6350 Stores Road
Vancouver, BC, Canada V6T 1Z4
dixon@interchange.ubc.ca
ABSTRACT
Although heap bioleaching has been recognized as an economic alterna-
tive for treating low grade mineral ores, the underlying physical, chemical
and biological processes involved are complex. A detailed investigation into
the dynamics of heap bioleaching processes has provided much insight into
the underlying complexities, and has led to the development of a sophisti-
cated modeling tool - HeapSim. This tool can be of great help in the design
and operation of heap bioleaching processes. In this paper, the mathemat-
ical model implemented in HeapSim is examined. The model takes into
account mineral kinetics, particle level effects, bacterial growth, oxidation
and adsorption, gas absorption, pore diffusion, bulk advection, gas balance
and heat conservation. Three case studies where the model has been applied
are briefly discussed.
INTRODUCTION
Copper in sulfide minerals is oxidized by reaction with ferric ions. The chemical
reactions between chalcocite, covellite and pyrite contained in the ore, and ferric in the
leaching solution, are of the form
R1. Cu2 S + 1.6Fe(SO4 )1.5 → 0.8CuSO4 + 1.6FeSO4 + 0.2Cu6 S5
R2. Cu6 S5 + 12Fe(SO4 )1.5 → 6CuSO4 + 12FeSO4 + 5S0
R3. FeS2 + [2+6(2 - β)]Fe(SO4 )1.5 + 4(2 - β)H2 O → [3+6(2 - β)]FeSO4 + 4(2 -
β)H2 SO4 + β S0
β above is the pyrite abiotic elemental sulfur yield. It represents the fraction of the
second (pyritic) sulfur atom in pyrite that is oxidized only to elemental sulfur rather
than sulfate. It varies between 0.0 and 1.0 depending on the redox potential [15].
The sulfur and ferrous produced in the reactions above undergo microbially
mediated oxidation to sulfate and ferric.
R4. 2S0 + 3O2 + 2H2 O → 2H2 SO4
R5. 4FeSO4 + O2 + 2H2 SO4 → 4Fe(SO4 )1.5 + 2H2 O
Reactions R4 and R5 are pivotal as they represent the microbial regeneration of ferric
and acid, and so facilitate reactions R1-R3. In addition to the reactions above, acid is
consumed by gangue, and jarosite is produced.
R6. H2 SO4 + MO → MSO4 + H2 O (M is a divalent metal ion).
R7. 6Fe(SO4 )1.5 + 14H2 O → 2H3 OFe3 (SO4 )2 (OH)6 + 5H2 SO4
Based on the these chemical reactions, the transportable species of interest in
the leaching solution are copper sulfate [CuSO4 ], ferrous sulfate [FeSO4 ], ferric sulfate
[Fe(SO4 )1.5 ], sulfuric acid [H2 SO4 ], sulfur oxidizers [mesophiles, moderate thermophiles,
extreme thermophiles] and iron oxidizers [mesophiles, moderate thermophiles, extreme
thermophiles].
The rate of each heterogeneous leaching reaction j is given by:
1 dgj gj,0 dXj
rj = = . (1)
s dt s dt
g is the grade of the mineral, and Xj is the conversion of reaction j, or the frac-
tion of a mineral that has reacted. In Eq.(1), division by s (stagnant liquid mass
fraction [kg(stagnant liquid)/kg dry ore]) rectifies the unit of the reaction rate to
[mol/kg(stagnant liquid)/s].
The rate of mineral conversion incorporates functions for the effect of tempera-
ture, solution composition and mineral topology,
dXj
= kj (T ) fj (C) Wj (1 − X) . (2)
dt
k(T ) is the rate constant given by Arrhenius law
E 1 1
k(T ) = k0 exp − − (3)
R T T0
where k0 is the rate constant at the reference temperature T0 .
The concentration function f (C) takes different forms depending on the electro-
chemical nature of the reaction. The form implemented in the model is
CF e3+
f (C) = (1−m)
(4)
(kA + CF e 3+ ) (k B + CF e2+ )m
where kA is the ferric mass transfer parameter and kB is the ferric reduction parame-
ter [15]. Eq.(4) can represent any one of the three most common forms of electrochem-
ical rate control depending upon the values of the two parameters kA and kB . When
both are zero (and m ≈ 0.5), then anodic mineral decomposition is rate-controlling.
When kA = 0 and kB CFe2+ , then ferric reduction is rate-controlling. Finally, when
kA CFe3+ and kB CFe2+ , then ferric mass transfer is rate-controlling.
The topological rate term W (1 − X) accounts for the change in reactive sur-
face area with time. Two classic models for fluid-particle reactions are the shrinking
core model and the shrinking sphere model [9]. Traditionally, these approaches have
been used in leach modeling, assuming relatively small, uniform and spherical particles.
However, their applicability to a coarse ore situation in a heap is limited since the par-
ticles are neither spherical nor of uniform size. Also, the topology of leaching is more
complex than these simple models allow. A generalized form is adopted,
W (1 − X) = (1 − X)φ . (5)
where KI,b is the growth-inhibition constant for bactrial species b and CI the concen-
tration of the growth inhibition factor. For CI KI,b , fI,b → 1 and growth-inhibition
is low. For CI KI,b , fI,b → 0 and growth-inhibition is high.
The death term in Eq.(7) depends on the temperature of the heap, assuming
that increasing temperature beyond a certain threshold will result in rapid microbial
death.
Acknowledging that kg is modified by the growth temperature fg (T ) (in other
words, microbial growth has an optimum temperature range, with reduced growth
outside this range), the death temperature fd (T ), and the endogenous decay factor ke ,
the following model for the change in microbial population is implemented:
dN
= N kgmax [fg (T ) (Π(1 + ke ) − ke ) − fd (T )] (10)
dt
where Y Y
Π= fL,i fI,j .
i j
where PO2 is the partial pressure of oxygen, and k(T, C) is the solubility of dissolved
oxygen at unit partial pressure [molal/atm]. k(T, C) may be written as the product of
the solubility of oxygen in pure water k ⊗ (T ), and a salting factor σ(C). σ(C) accounts
for the decrease in oxygen solubility due to the presence of salts in solution [6], but is
not considered in the model. The solubility of oxygen in pure water takes the form:
A + BT + CT 2 + DT ln T
⊗
k (T ) = exp (15)
RT
where A,B,C,D are empirical constants and R is the gas constant [6].
The rate of dissolved oxygen production is modeled as
The rate of acid consumption by gangue is modeled by a first order rate law in
the concentration of sulfuric acid,
SOLUTE TRANSPORT
The heap is conceptually divided into columns (Fig.1). As copper heaps are
conventionally run under dripper emitters, it is assumed that the drippers trace out the
perimeter of identical cylindrical columns, so that one can model the heap by considering
a single cylindrical column. A column is divided into bulk flow channels, and equal-
length diffusion side branches (profile side pore diffusion model with fixed pore length
[1]). Intra-particle, inter-particle and inter-agglomerate porosities are combined to form
a single pore. Pore length is approximated by half the distance between drippers.
Transport of dissolved species is by advection along bulk channels, and by diffusion
through the stagnant pore. The diffusion driving force from the flowing liquid is assumed
to be greater than the concentration gradient between adjacent pores at all times.
Hence, there is no diffusion between individual side-branches [1].
The transportable species were mentioned in the previous section. Mass balance
for a species i along a diffusion pathway (stagnant pore) is described by the continuity
equation for mass transport,
2
1 Si ∂Ci ∂ Ci 1 ∂Ci
1+ = Di + + Γi . (20)
s Ci ∂t ∂r2 r ∂r
S is the adsorbed microbial concentration ([cell mole/kg dry ore]). The 1/s factor
rectifies the unit of S to [cell mole/kg stagnant liquid]. The adsorbed fraction S i /Ci
is taken as zero for the chemical species, and calculated from the Langmuir adsorption
model for the microbes:
Si Si,max KL,i
= . (21)
Ci 1 + KL,i Ĉi
Si,max is the maximum number of bacteria that can adsorb per kg of ore, and KL is the
adsorption equilibrium constant.
Γi , the component generation rate of species i, is given by
X
Γi = νij rj for chemical species (see Eq.(1))
j
= Eq.(10) for bacterial species . (22)
Drippers
Diffusion
Channel
Advection
Channel
Ore heap
ζ=0
Advection
Channel
Diffusion
Channel
Bulk flow
The heat transport model is important in copper sulfide leaching because the
bacteria that catalyze the oxidation reactions are sensitive to temperature. Further-
more, the rates of key reactions in the heap are temperature dependent. A complete
derivation and exhaustive discussion of the heat transport model is available in [4].
Only an overview is given in this section.
Heat transport in the heap is via
• conduction through the solids and stagnant solution.
• convection by the leaching solution flowing downwards and the gaseous phase
(including water vapor) flowing upwards.
A general enthalpy balance is written as
In dimensionless form:
1 ∂2T
∂T Ff (T ) Fv (T ) ∂T
= − − + Q̃ . (34)
∂t τc ∂ζ 2 τf τa ∂ζ
τc , τf and τa are conduction, liquid phase advection and gaseous phase advection
timescales respectively, given as
Q
Q̃ = . (37)
(ρcp )h
1 ∂T 1 n o
− = [1 + βωa ψ(Ta )][T ζ=1 − Ta ] + κ[ψ(T ζ=1 ) − ωa ψ(Ta )] (42)
τc ∂ζ ζ=1 τa
Eq.(41) accounts for heat flux at the surface of the heap, and heat gain due to the
application of the leaching solution. Eq.(42) accounts for heat loss due to the saturation
(with water vapor) of air applied to the base. The flux term is written
P
X q
q̃ = (43)
(ρcp )h Z
where
X
q = qconvection + qevaporation + qradiation (44)
qconvection = h[T∞ − T ζ=0 ] Newton’s law of cooling (45)
qevaporation = −kg ρa [ψ(T ζ=0 ) − ω∞ ψ(T∞ )] Newton’s law of cooling (46)
qradiation = αs G(z) − ε F1→2 σ[T 4 4
ζ=0
− Tsky ] Stefan’s law (47)
Here G(z) is intensity of solar radiation for the zenith angle z, T∞ is the ambient
temperature, and Tsky is the effective blackbody sky temperature.
The transport of oxygen through the heap is included through a 1-D model for
its partial pressure. The following assumptions are made [15] :
• The overall flow of dry air is not significantly diminished by the consumption
of oxygen (Boussinesq approximation).
• The diffusion of oxygen is negligible compared to advection.
• Steady state may be safely assumed (Net rate of oxygen input by advection
equals net rate of oxygen consumed).
The steady state equation is
∂ G g C O2
= s rO2 ρh , (48)
∂z ρg
where CO2 is in [mol/m3 ]. Noting the Boussinesq approximation, the gas mass flux is
written as
Gg = Ga (1 + ψ) . (49)
Also from ideal gas law , the gas density and concentration are written as
P g Mg P O2
ρg = ; C O2 = . (50)
RT RT
Mg here is the molar mass of the gas. Substituting these in Eq.(48) gives
Ga ∂ 1 + ψ
P O2 = s rO2 ρh . (51)
Pg ∂z Mg
P g s ρh rO2 ψ 0 ∂T
− PO
∂PO2 Ga Mv ∂z 2
= . (53)
∂z 1 ψ
+
Ma Mv
z
Expressing distance in dimensionless form (ζ = )
Z
Zρh Pg s rO2 ψ 0 ∂T
− PO
∂PO2 Ga Mv ∂ζ 2
= . (54)
∂ζ 1 ψ
+
Ma Mv
The boundary condition for Eq.(54) at the heap base is
!
M v
PO2 ζ=1 = 0.21 P∞ (55)
Mv + M a ψ ζ=1
MODEL APPLICATIONS
The heap bioleaching model derived above has been applied to case studies of
chalcocite, chalcopyrite and zinc sulfide leaching. The model parameters used in the
simulations are either measured for each case study (for instance the kinetic parame-
ters), or adapted from literature (for instance some microbial parameters).
In [14, 16], column experimental results are compared with model predictions
for chalcocite leaching. The model confirms the two-stage chalcocite leaching process
observed in experiments. Simulation results show that first-stage leaching progresses
in a narrow band which moves down the column, while second-stage leaching is more
homogeneous across the entire column depth. It is further deduced from the model that
the full scale heap chalcocite leaching is limited by the rate of acid supply to reaction
sites due to an increased effective diffusion path length.
In [13, 14], thermophilic leaching of chalcopyrite is investigated using the
geocoatTM process, in which the ore particle is spray-coated with ore concentrate
in order to maximize mineral exposure. Results from the model suggest that heating a
heap to the thermophilic range and maintaining it there is unproblematic, although this
requires the presence of another reactive sulfide such as pyrite to generate the initial
heat. Furthemore, model results show that temperatures over the heap are not uniform
even at steady state conditions. It also shows that dissolved oxygen levels calculated
from Eq.(48) are low throughout, suggesting that the rate of oxygen mass transfer from
gas to liquid phase is the overall rate limiting step.
Modelling work done on zinc sulfide [11, 12] suggests that the most important
parameters to zinc extraction rate are the heap height, irrigation rate, feed acid concen-
tration, and side branch length. Their significance arises because the heap is partially
limited by the supply and diffusion of sulfuric acid. Other important parameters are
the rate of oxygen mass transfer from gas to liquid, and the feed solution temperature.
CONCLUSIONS
NOMENCLATURE
Greek Letters
αs Heap surface solar absorptivity
Liquid mass fraction kg water/kg dry ore
Γ Specie generation rate molal/s
λ Latent heat of vaporization kJ/kg
ν Stoichiometric factor
ω Relative humidity
ψ Saturation humidity
ρ Density kg/m3
σ Stefan-Boltzmann constant 5.67 x 10−8 W/m2 /K4
τ Tortuosity factor
ε Heap surface grey body emissivity
ξ Dimensionless diffusion pathway length
ζ Dimensionless heap height
Roman Letters
k Average heap thermal conductivity W/m/K
R̃ Effective diffusion pathway length (τ R) m
C Concentration molal
cp Heat capacity J/kg/K
D Diffusivity m2 /s
E Activation energy J/mol
F1→2 Heap-to-sky view factor
G Mass flux kg/m2 /s
g Grade mol/kg dry ore
h Heap surface heat transfer coefficient W/m2 /K
kA Ferric mass transfer parameter molal
kB Ferric reduction parameter molal
ke Endogenous decay factor
kg Mass transfer coefficient , see equation (38) kg/s
kg Microbial specific growth rate , see equation (8) s−1
KL Langmuir adsorption constant molal−1
kL a Gas-liquid mixing coefficient s−1
12
km Specific maintenance rate mol/10 cells/hr
kacid Gange-acid rate constant m3 /mol/s
kJ Jarosite precipitation equilibrium constant
KI,b Growth inhibition constant for species b cell molal
KL,b Monod constant for species b molal
m Exponent in electrochemical law , see equation (4)
N Microbial population 1012 cells/kg dry ore
P Pressure atm
Q Heat generation rate from chemical reactions W/m3
q Heat flux W/m2
R Diffusion pathway length m
R Universal gas constant 8.314 J/mol/K
r Formula rate molal/s
S Adsorbed microbial concentration 1012 cells/kg dry ore
T Temperature K or ◦C
uf Flowing liquid superficial velocity m/s
X Mineral conversion
y Specific cell yield 1012 cells/mol
Z Heap height m
Subscripts
∞ Ambient condition
a Dry air
f Flowing liquid
h Heap
s Stagnant liquid
v Water vapor