Analysis of biological and metallurgical

factors which can control copper leaching

rate in bioleaching operations
Toms Vargas
Center of
Hydrometallurgy/Electrometallurgy/Biohydrometallurgy
University of Chile
Bioleaching of copper sulfides in dumps and heaps
is to day a well established technology.
First dump leaching operations: Rio Tinto, Spain;
Cananea, Mexico (60-70s)
The first plant to bioleach secondary copper
sulfides in heaps was built in Lo Aguirre, near
Santiago, in 1990 (approx) with the technology
developped by the R&D group of Minera Pudahuel,
a Chilean company.
Today Chile concentrates more that 50% of world
copper produced with this technology (J.Brierley,
IBS 2011)
PLANTA TRES VALLES, 30.000 TON CU CATHODES, VALE (2010)
Bacteria
Cu
+2
Fe
+2
Fe
+3
CuS
LIXIVIACIN BACTERIANA EN PILAS
BIOLEACHING OF COPPER SULFIDES
with permission of
VALE S.A:
However, there are too many expectations about the impact of the addition of
inocula or the improvement of oxidative capacity of microorganisms (by genetics
or adaptation), on the rate of copper leaching
Leaching time
C
o
p
p
e
r

r
e
c
o
v
e
r
y
,

%


(
$
$
$
$
)
100
Abiotic system
+ bact
++ bact
+++ bact
THERE IS A CONSTANT SEARCH FOR FASTER LEACHING RATES AND BETTER
COPPER RECOVERIES
When inoculation or improvement of
bacterial activity could be of any benefit?:
It would be of any benefit only in conditions in
which the rate of dissolution of the sulfide is
limited by the oxidative activity of
microorganisms
To define this is not a microbiological
problem: it demands a global view of the
process, pondering simultaneously biological
and metallurgical factors.
Fe
+3
+ e- Fe
+2
O
2
+ 4H
+
+ 4e- 2H
2
O
Cu
+2
+ S
0
+ 2e CuS
+ 1.229
+ 0.77
+ 0.55
e-
e-
Flow of electrons in dissolution of sulfides under
bacterial catalytic action
bacteria
4
2
2
2
ln
4
229 . 1
+
+ + =
H
O
O H
O
c p
F
RT
E
SOME FUNDAMENTAL ASPECTS
Fe
+3
Fe
+2
H
+
, O
2
H
2
O
Cu
x
S
e-
O
2
, CO
2
(Solution)
Electron transport in the bioleaching of sulfides in the presence of
Fe
+2
, Fe
+3
ions
T.f.
Cu
+2
THE CORE REACTIONS
H
2
SO
4
Air:
O
2
, CO
2
CuOx
Cu
4
(OH)
6
SO
4
FeO
x
Fe
3+
Fe
2+
Clays
Q
Cu
2+
Gangue
H
2
SO
4
S
0
Cu
2
S
CuS,CuFeS
2
Cu
5
FeS
4
FeS
2
Fe
3+
At.f.
T.f.
At.f.
Lept.f
Fe
3+
Fe
2+
Cu
2+
Clays
Fe
2+
H
2
O
(Q)
Jarosites
H
2
O
H
A FULL PICTURE IS NECESSARY
Fe
+2
, H
+
, O
2
Fe
+3
Fe
+3
Fe
+2
SULFIDE
BACTERIA
H
+
O
2
Fe
+3
+ MS Fe
+2
+ Cu
+2
+ S
0
4Fe
+2
+ O
2
+ 4H
+
4Fe
+3
+ 2H
2
O
A SIMPLIFIED BUT USEFUL SCHEME
Fe
+2
, H
+
, O
2
Fe
+3
Fe
+3
Fe
+2
SULFIDE
BACTERIA
H
+
O
2
CASES WHERE INOCULATION WOULD
NOT BE OF ANY ADVANTAGE:
A: CONTROL BY ACID SUPPLY
BIOLEACHING OF EL TENIENTE CRATER: A CASE CONTROLLED BY
ACID SUPPLY
EFFECT OF ACID CONCENTRATION IN FEEDING SOLUTION
Time, weeks
A
c
i
d

c
o
n
c
e
n
t
r
a
t
i
o
n
,

g
/
l
Time, weeks
S
o
l
u
t
i
o
n

p
o
t
e
n
t
i
a
l
,

m
V

v
s

A
g
/
A
g
C
l
OXIDATIVE POTENTIAL IN EXIT SOLUTION
Time, weeks
B
a
c
t
e
r
i
a

i
n

s
o
l
u
t
i
o
n
,

b
a
c
t

x

1
0
-
6
/
s
MICROORGANISMS IN EXIT SOLUTION
Time, weeks
C
o
p
p
e
r

i
n

s
o
l
u
t
i
o
n
,

g
/
s
COPPER IN EXIT SOLUTION
SYSTEM CONTROLLED BY ACID SUPPLY: INOCULATION WOULD NOT BE
OF ANY BENEFIT IN THIS CASE
CONTROL BY H
+
DIFFUSION IN HEAPS
(Petersen and Dixon, 2003)
Leaching time
C
o
p
p
e
r

r
e
c
o
v
e
r
y
,

%

Long dripper spacing
Short dripper spacing
H
+
Fe
+2
, H
+
, O
2
Fe
+3
Fe
+3
Fe
+2
SULFIDE
BACTERIA
H
+
O
2
CASES WHERE INOCULATION WOULD
NOT BE OF ANY ADVANTAGE:
B: CONTROL BY OXYGEN SUPPLY
e
-
e
-
O
2
, H
+
Fe
2+
Fe
3+
CuS
2 m
O
2
Fe
3+
Fe
2+
Fe
3+
+ Cu
x
S

Fe
2+
+ S
0
+ x Cu
2+
H
2
O
COPPER BIOLEACHING IN HEAPS WITH AIREATION BY NATURAL
CONVECTION: A CASE OF CONTROL BY OXYGEN SUPPLY
R. Montealegre et al. (1995), Copper 95, Santiago, Chile
EFFECT OF FORCED AIREATION
T. Lancaster and D. Walsh (1997), IBS-1997, Melbourne, Australia.
G= 1.7 [L/m^2-min]
0
1
2
3
4
5
6
0 5 10 15 20 25
P
r
o
f
u
n
d
i
d
a
d
,

[
m
]
G= 4.2[L/m^2-min]
0
2
4
6
0 5 10 15 20 25
P
r
o
f
u
n
d
i
d
a
d
,

[
m
]
G= 6.5[L/m^2-min]
0
2
4
6
0 5 10 15 20 25
P
r
o
f
u
n
d
i
d
a
d
,

[
m
]
Oxygen profiles as a function of heap height at three aeration rates. H.M.
Lizama. Int. J. Miner. Process. 62 (2001) 257269
h
e
i
g
h
t
,

m
h
e
i
g
h
t
,

m
h
e
i
g
h
t
,

m
oxygen in air (OA), %
EFFECT OF AIR FLOW ON THE INCREASE OF COPPER RECOVERY OVER
THE BASAL CASE OF NATURAL AIREATION
H. Salomon (2000), Learned lessons in high altitude leaching, Expomin, May
2000, Santiago, Chile
O2 , CO2
CLUSTERS OF PARTICLES IN
STAGNANT SOLUTION ZONES
HOWEVER, OVER CRITICAL AIR FLOW (~10 L/min m
2
) SYSTEM CAN STILL
BE CONTROLLED BY SUPPLY OF OXYGEN OR CO
2
TO REACTION ZONE
Fe
+2
, H
+
, O
2
Fe
+3
Fe
+3
Fe
+2
SULFIDE
BACTERIA
H
+
O
2
CASES WHERE INOCULATION COULD BE OF ANY ADVANTAGE:
GOOD SUPPLY OF ACID, OXYGEN AND, CO2
Fe
+2
, H
+
, O
2
Fe
+3
Fe
+3
Fe
+2
SULFIDE
BACTERIA
M
+n
[MS]
(X)
] [
] [
* 1
2
3
2
+
+
+
=
+
Fe
Fe
K
X v
v
Max
Fe
[ ]
] [
] [
1
3
2
max
2
+
+
+
+
= = +
Fe
Fe
B
MS v
bv v
MS MS
MS Fe

Rate of Fe
+2
consumption by bacterial oxidation (-v) and rate of chemical leaching
of MS, expressed as rate of Fe
+2
generation by reduction of Fe
+3
during leaching
of MS (+v), expressed as a function of Eh.
0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9
Solution Eh, V(SHE)
X
4
X
3
X
2
X
1
-v
Fe+2, bact
+v
Fe+2, chem

0
MS

3
MS

2
MS

1
MS
[ ]
] [
] [
1
3
2
max
2
+
+
+
+
= = +
Fe
Fe
B
MS v
bv v
MS MS
MS Fe

] [
] [
* 1
2
3
2
+
+
+
=
+
Fe
Fe
K
X v
v
Max
Fe

MS
(t)
X(t)
0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9
Solution Eh, V(SHE)
X
4
X
3
X
2
X
1
-v
Fe+2, bact
+v
Fe+2, chem

0
MS

3
MS

2
MS

1
MS
SMALL N MICROORGANISMS HIGH
REACTIVITY OF MS: INOCULATION
HAS A IMPACT
LARGER N MICROORGANISMS SMALLER
REACTIVITY OF MS: INCULATION DOES
NOT HAVE AN IMPACT
THE RATE OF COPPER SULFIDE LEACHING IS CONTROLLED BY
BACTERIAL ACTIVITY WHEN V
max
X < V
MS
max
. AFTER THAT BACTERIAL
INOCULATION IS OF NO USE
AN APPLICATION:
EVOLUTION OF COPPER,
PLANCTONIK BACTERIA, Eh
AND pH DURING
BIOLEACHING OF A COPPER
CONCENTRATE WITH A.
ferrooxidans
From: J. Casas (1991), M.Sc.
thesis in Chemical Engineering,
University of Chile.
time, days
With adequate data on
kinetics of +v
Fe+2
and v
Fe+2
it
is possible to model the
impact of bacterial population
on copper sulfides
bioleaching
bact. population
Fe
+3
Cu
+2
L. Lufin, 2007
A CASE CONTROLLED BY MICROBIOLOGICAL ACTIVITY:
BACTERIAL ACTIVITY INHIBITION DUE TO MISSMANAGEMENT OF
SOLUTION CHEMISTRY :
Al
2
(SO
4
)
3
MnSO
4
H
2
SO
4
CuSO
4
Fe(SO
4
)
x
H
+
Cu
2+
Al
2
(SO
4
)
3
MnSO
4
H
2
SO
4
CuSO
4
Fe(SO
4
)
x
AlO
x
MnO
x
CuO
x
FeO
x
CaO
x
CaSO
4
(p
pt)
H
2
SO
4
LEACHING SOLVENT
EXTRACTION
SOLUTION
REMAINING IN
LEACHED ORE
JAROSITES PRECIPITATION,
GYPSUM PRECIPITATION, ETC.
ORGANIC
C1 C2 C3
[ SO
4
2-
, Xi
+
]

max
BACTERIAL INHIBICION DUE TO
HIGH IONIC CONCENTRATION
1.0
0
CONCLUSIONS
Improvement of bacterial oxidative activity (X x
max
)
through inoculation (larger X) or by adaptation/genetic
modification (larger
max
) could have any impact on copper
leaching rate only if there is good supply of solution,
H
+
,O
2
and CO
2
to reacting sites.
Inoculation of the ore would be of any benefit only in
conditions in which the rate of dissolution of the sulfide is
limited by the oxidative activity of microorganisms. The
impact of inoculation can be assessed in advanced in this
case from kinetic data of biological ferrous iron oxidation
and copper sulfide leaching, using modelling.
Unless there are strong inhibitig conditions, the system will
be rearly controlled by bacterial oxidative activity.
Questionable to claim advantages for some particular
microorganisms
Fe
+2
Fe
+3
Fe
+3
(FeO
X
)
Cu
+2
SO
4
-2
S
2
-2
S
0
CHALCOPYRITE
SUBPRODUCTS
LAYER
SOLUTION
Cu
+
Fe
+3
CuO
X
e
Fe
+3
?
IDEAL SITUATION: COPPER LEACHING RATE CONTROLLED BY THE
INTRINSIC RATE OF SULFIDE DISSOLUTION
THE QUESTION REMAINS: HOW MUCH CAN MICROORGANISMS DO TO
HELP AT THAT LEVEL
CuFeS
?
?
?
?
?
DIRECT CATALYTICAL ACTION PREVENTED BY PHYSICAL
CONSTRAINTS
THANK YOU