Hydrometallurgy 87 (2007) 100 – 111

www.elsevier.com/locate/hydromet

La biolixiviación de un calcopirita concentrado con microorganismos termófilos

moderados en un sistema de reactor continuo

L. Cancho, ML Blázquez •, A. Ballester, F. González, JA Muñoz

Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica, Universidad Complutense de Madrid, España

Recibido el 28 de junio de 2006; recibida en el formulario EASA 14 de diciembre de de 2006 revisado; aceptado el 19 de de febrero de de 2007

Disponible en línea el 21 de marzo de de 2007

Abstracto

The metal extraction efficiency of bioleaching processes can be greatly improved by using stirred-tank reactors. However, owing to the high cost of acquiring and
maintaining these, their use is restricted to the treatment of high-grade ores and concentrates. Unlike gold, the copper industry is not far from achieving commercial
implementation of stirred processes on an industrial scale. Recent research has focused on the development of continuous bioleaching processes for the treatment
of copper flotation concentrates.

The aim of the present work was to optimize a process for continuous bioleaching of chalcopyrite concentrates using moderate thermophilic microorganisms and
silver ions. The best results were obtained using a series of three reactors under the following experimental conditions: 45 °C, 14 days residence time, 2 g Ag/kg of
concentrate (silver deposition stage at 35 °C), stirring rate adjusted to 350 rpm, pH between 1.2 and 1.4 and redox potential between 400 and 500 mV vs. Ag/AgCl.
The optimized continuous bioleaching system was able to dissolve copper steadily at a concentration higher than 11 g/L. © 2007 Elsevier B.V. All rights reserved.

Keywords: Copper flotation concentrate; Continuous bioleaching; Moderate thermophilic microorganisms; Silver catalysis

1. Introduction technologies and processes have shown promising results on both

The aerated stirred reactor improves both the yield and the
efficiency of bioleaching processes. The higher costs associated with
the manufacture and maintenance of these vessels restrict their use
to the treatment of highgrade ores and concentrates. Most of the
existing commercial plants that work with stirred bioreactors recover
gold from arsenopyrite concentrates.
Unlike gold, the commercial implementation of this process for the
recovery of copper from concentrates is still in its infancy. However, in
the last few years several
• Corresponding author. Tel.: +34 91 394 4339; fax: +34 91 394 4357.
laboratory and pilot scales.
The IBES (Indirect Bioleaching with Effects Separation) and
BRISA ( Biolixiviación Rápida Indirecta con Separación de Acciones: Fast
Indirect Bioleaching with Actions Separation) processes have been
developed at the University of Seville (Seville, Spain) for the
treatment of chalcopyrite in the former case, and secondary copper
sulphides such as chalcocite and covellite, in the latter ( Carranza et
al., 1997; Palencia et al., 2002 ). In both processes, the
silver-catalysed chemical stage (leaching) is performed separately
from the biological stage (bioxidation), in such a way that the high
ferric concentrations produced by bacteria in the first reactor can later
be used to dissolve the mineral.

E-mail address: mlblazquez@quim.ucm.es (M.L. Blázquez).

0304-386X/$ - see front matter © 2007 Elsevier B.V. All rights reserved. doi: 10.1016/j.hydromet.2007.02.007
 L. Cancho et al. / Hydrometallurgy 87 (2007) 100 – 111
In 1998, a one-year stirred-tank bioleaching pilot test conducted at
the copper mines in Mt. Lyell, Tasmania (Australia) demonstrated the
technical and commercial feasibility of copper concentrate bioleaching
with moderate thermophilic microorganisms ( Rhodes and Deeplaul,
1998; Brierley and Brierley, 1999 ). En el marco del Programa de
Investigación de la Unión Europea, un grupo de socios europeos
(BRGM, Francia; Universidad ofWarwick andMIRO, Reino Unido;
Boliden, Suecia y Cognis, Alemania) trabajado bajo la oxidación
bacteriana proyecto de alta temperatura, HIOX® 1996-1999 . el
objetivo de este proyecto era poner un nuevo microorganismo
termófilo para la biolixiviación de concentrados de calcopirita a utilizar
mediante la propuesta de un proceso industrial económico y
ecológico para la recuperación de cobre. Se han realizado varios
estudios de calcopirita biolixiviación continua utilizando
microorganismos termófilos extremos en este proyecto. Los
resultados fueron muy prometedores, con la extracción de cobre
superior a 90% en 5 días de residencia y una densidad de pulpa de
12% ( d'Hugues et al., 2002 ).
Recent research in bioreactors has shown promising results on
the bioleaching of copper flotation concentrates with mesophilic
microorganisms ( Sadowski et al., 2003 ).
An excellent example of the increasing importance of stirred-tank
bioleaching was the creation of a new consortium, Alliance Copper
Limited (ACL), between Codelco and BHP Billiton ( Batty and Rorke,
2006; Clark et al., 2006 ). This company pioneered bioleaching of
copper concentrates in stirred tanks, a new technological departure
that led to changes in the practice of the mining industry. In 1997, the
new company started a pilot plant in Chuquicamata (Chile) which
worked for 4 years, although presently the continuity of the project is
being reconsidered.
La mayoría de las plantas comerciales existentes y plantas previstas
utilizan microorganismos termófilos mesófilas o moderados con un rango
de temperatura de crecimiento entre 40 y 50 ° C. Un caso atípico es el
reactor industrial semi-comercial (300 m 3) diseñada por BHP Billiton en
África del Sur, que opera a temperaturas superiores a 60 ° C y se
construyó para determinar los criterios de diseño más adecuados para la
planta piloto Alliance Copper Ltd., en Chile. Otro caso es el proceso
compartido por Mintek-BacTech y Peñoles en México ( Rawlings et al.,
2003 ). Ellos desarrollaron conjuntamente un proceso de biolixiviación
tanque hasta el nivel de la planta de demostración en la operación de
Peñoles. El proyecto se centró en un polimetálica (calcopirita, esfalerita,
galena) concentrado que contiene metales preciosos. Las recuperaciones
de 96 - 97% de Cu, 99% de Zn, 98 - 99% de Au y 40% de Ag se logra a una
velocidad de alimentación de
101
2.7 t/day. This plant is designed to operate at temperatures exceeding
60 °C and produce 500 kg/day of copper cathodes by a SX/EW
process ( Olson et al., 2003; van Staden et al., 2003 ). In general, the
principal objective of a bioleaching study is to overcome the main
drawback of the process scale-up: the low kinetics. In the case of
chalcopyrite, the studies indicate formation of a passivating film on
the surface during dissolution, which prevents direct contact between
the solution and the mineral and limits the electrochemical transport
required for the electrochemical dissolution mechanism to act ( Tshilombo
and Dixon, 2003; Sandström et al., 2005 ). Una de las soluciones más
comunes a este problema, y ​a la lenta cinética de los procesos de
biolixiviación en general, es elevar la temperatura. Sin embargo, el
uso de microorganismos termófilos extremos puede presentar una
serie de dificultades, tales como: baja solubilidad del oxígeno en
agua; estos microorganismos son menos resistentes a altas
concentraciones de metal y a los catalizadores como la plata, y
presentan una menor resistencia mecánica que microorganismos
mesófilos a la atrición de su membrana. Por otra parte, las
reacciones de lixiviación son exotérmicas, elevando la temperatura
de tanques agitados a 40 - 50 °C, which is the optimum range for the
growth of moderate thermophilic microorganisms. In many cases,
industry has preferred these moderate thermophilic microorganisms
because they are more resistant to higher pulp densities and higher
heavy metal concentrations than extreme thermophiles ( Okibe et al.,
2003; Olson and Clark, 2004 ). Because large amounts of mineral are
treated by bioleaching and bioxidation, it would be more profitable to
operate in continuous mode in stirred-tank reactors with higher
volumetric productivity and lower maintenance costs. In view of these
considerations and the kinetics of bacterial growth, continuous stirred
reactors are the best option for this kind of treatment.
The basis for selection and design of the most suitable reactor for
a biomining process must be the physical, chemical and biological
characteristics of the system. Special attention should be given to the
complex nature of the pulp, which consists of an aqueous solution
with cells in suspension and adhering to the mineral, and also a
suspended solid and air bubbles ( Gormely and Brannion, 1989;
Acevedo, 2000 ). Yet another alternative in chalcopyrite bioleaching is
the use of silver as a chemical catalyst. Copper recovery from
chalcopyrite has been improved through the use of silver as a
catalyst in both chemical and biological leaching systems, and the
reaction mechanisms (1) –( 2) involved are apparently identical in both
cases: in the presence and the absence of bacteria ( Ballester et al.,
102 L. Cancho et al. / Hydrometallurgy 87 (2007) 100 – 111
1990; Gómez et al., 1999 ). Silver interacts with chalcopyrite as
follows:
CuFeS 2 þ 4Ag þ → 2Ag 2 S ð chalcopyrite surface Þ
þ Cu 2 þ þ Fe 2 þ
Silver sulphide is formed on the mineral surface by means of a
chemical reaction involving an interchange between the silver and the
copper and iron from the chalcopyrite lattice. The silver sulphide
dissolves in the presence of an oxidizing agent such as ferric ion:
Ag 2 S þ 2Fe 3 þ → 2Ag þ þ 2Fe 2 þ þ S 0
In bioleaching, the bacteria play an indirect role in the process,
facilitating the oxidation of Fe 2+ to Fe 3+ and depolarizing the cathodic
half-reaction in accordance with: 2 FeSO 4 þ 0:5O 2 þ H 2 SO 4 → Fe 2 ð SO 4 Þ chalcopyrite (CuFeS 2) as the main phase, and pyrite (FeS 2), sphalerite
3þ H2 O ð 3 Þ
Reaction (3), plays an important role in the process. When the
bacterial activity decreases, the ferrous ion is not oxidized to ferric ion
and the dissolution of chalcopyrite is halted or continues at a very
slow rate.
The regeneration of Ag+ gives rise to a cyclic process that
increases the rate of copper dissolution. The silver effect is enhanced
in the presence of iron and sulphur oxidizing microorganisms. On the
one hand, bacteria maintain a favourable Fe 3+/ Fe 2+ ratio, contributing
to oxidation and, on the other hand, microorganisms oxidize the
elemental sulphur layer produced on the chalcopyrite surface in
reaction (2), preventing chalcopyrite passivation:
Microorganism H 2 SO 4
S 0 þ H 2 O þ 3=2O 2 Y
The reaction of silver with mineral sulphides other than
chalcopyrite has also been considered in the bioleaching process. Ahonen
and Tuovinen (1990) reported that the leaching of zinc from sphalerite
and iron from pyrite in a complex sulphide ore was inhibited by silver
addition. Similarly, Nakazawa et al., using a flotation concentrate
containing chalcopyrite and pentlandite, observed catalysis of silver
on the bioleaching of chalcopyrite but not of pentlandite, with
increasing initial silver concentrations ( Nakazawa et al., 1993 ).
Table 1
Origin, chemical composition and particle size of RT concentrate Origin
Cu % Fe %
Río Tinto (Huelva, Spain) 22.44 31.20
The aim of the present work was to optimize a process for
continuous bioleaching of chalcopyrite concentrates with moderate
thermophilic microorganisms and silver. To that end, different
variables were studied (residence time, silver concentration, stirring,
ð1Þ
redox potential and temperature) to obtain copper concentrate
solutions.
2. Materials and methods
2.1. Mineral concentrate
ð2Þ
A differential flotation chalcopyrite concentrate, named RT, was
used (for origin and chemical composition see Table 1 ).
X-ray diffraction of mineral RT showed the presence of
(ZnS) and silica (SiO 2) as minority phases.
2.2. Bacterial culture
The culture was one of moderate thermophilic microorganisms
(named TMRT) grown from acid mine drainage from Río Tinto
(Huelva, Spain). The culture was composed mainly of S-oxidizing
bacteria with ability to oxidize different sulphide minerals, especially
copper sulphides. An important feature of the culture was that its
heavy metal resistance at low pH was higher than that of other
moderate thermophiles described in the literature. Moreover, the
culture also contained different Fe-oxidizing microorganisms, but in
smaller proportions ( Gómez et al., 1999 ). Particularly important in this
culture was the moderate thermophilic microorganism named TMRT,
isolated by the Extractive Metallurgy research group at the
Complutense University of Madrid ( Gómez et al., 1997 ). This is an
ð4Þ aerobic bacterium, strictly chemolithoautotrophic, with the ability to
oxidize reduced sulphur compounds.
The culture was grown in an orbital shaker at 45 °C, pH 1.5 and
150 rpm in Norris medium, modified without iron ( Norris et al., 1986 ),
with the following chemical composition: 0.4 g/L MgSO 4 7H 2 O; 0.2 g/L
(NH 4)2 SO 4
and 0.1 g/L K 2 HPO 4. The RT concentrate was used as energy
substrate at a pulp density of 5%w/v. The culture was also adapted to
different amounts of silver (0.3, 0.6,
Zn % Pb % S% Particle size
2.70 0.02 38.79 b 105 μ m (95%)
 L. Cancho et al. / Hydrometallurgy 87 (2007) 100 – 111
1 and 2 g Ag/kg concentrate) under different experimental conditions.
In the silver-catalysed bioleaching tests, the appropriate amount of
Ag+ was added to the pulp before adding the bacterial inoculum.
2.3. Continuous bioleaching set-up
Fig. 1 shows the continuous bioleaching set-up used. This
consists of a feeding tank (A), a peristaltic pump (B) to supply fresh
pulp to the first of three mechanically stirred (M) reactors in cascade
(R-1, R-2, R-3), and a collector for the final product (P). The pulp was
transferred by overflow from tank to tank.
In the first three continuous bioleaching experiments, all the tanks
including the feeding tank had an effective capacity of 2.4 L. The
reactors were thermostatted and closed to avoid evaporation of the
solution. Temperature was controlled with a thermocouple (T). The air
supply for bacterial growth (500 mL/min) was controlled by differential
water manometers (D) and injected into the reactors through glass
capillaries (O). Flasks (F) were placed between both devices to
prevent the backward of the liquid. The last test was performed in an
improved system. The improvement chiefly affected the stirring
system, in which baffles were used and a flow of air was supplied
from the base of the reactor. Additionally, the
Fig. 1. Continuous bioleaching set-up.
103
first reactor (6 L) was twice the volume of the second and third reactors
(3 L) in order to increase the residence time and to encourage
adaptation of the microorganisms.
2.4. Experimental procedure
All the continuous experiments were preceded by a discontinuous
stage designed to adapt the culture to the test conditions. Once each
reactor was inoculated, metal concentration in solution (Cu, Fe, Zn),
pH, redox potential and bacterial population were measured. The
continuous feed was started once the optimum culture growth was
attained. The pulp density was 5% in all tests.
Evaporation was restored periodically with distilled water, pH
controlled and adjusted (with sulphuric acid 20% v/v) to below 1.5;
redox potential was measured (vs. Ag/AgCl) and a sample was
removed to determine i) the number of cells in the liquid phase using
a Thoma counting chamber (depth 0.1 mm) with a phase-contrast
microscope, and ii) iron and copper concentration using atomic
absorption spectrophotometry.
The end of the experiment in each reactor was reached when the
bacterial population and the amount of dissolved metal stabilized. The
overall yield was determined by mass balance of the solid residues
and the feeding solutions, in each reactor and in the
104 L. Cancho et al. / Hydrometallurgy 87 (2007) 100 – 111

collector. This balance is expressed by the following equation:

Metal Fed ¼ Metal R 1 þ Metal R 2 þ Metal R 3 þ Σ Metal Pi

Los principales errores asociados con este equilibrio son la pérdida de

sólidos durante la filtración y la pérdida de líquido en los pasteles. Ese error se
calcula como una función de la diferencia entre los dos términos de la igualdad.

3. Resultados y discusión

La variación de la concentración de metales (g / L), pH y el potencial

redox en los reactores de tanque (R-1, R-2 y R-
3), en el tanque de alimentación (A) y en el colector (P) se muestra para
cada prueba. Los resultados representados en la porción inicial de cada
figura ( Higos. 2 - 9 ) Ilustran la fase por lotes (discontinua) del experimento.

At the beginning of the continuous tests, the metal concentration

in solution and the cell population diminished. This indicates that the
gradual increase of metal concentration observed during the previous
discontinuous stage was a result of bacterial action. However, once
the continuous test started, the feeding of fresh pulp into reactor R-1
and the output of concentrated solution from reactor R-3 produced a
diluting effect, reducing the metal concentration in each reactor.

In the continuous experiments, the optimum residence time was

determined by the stabilization of metal concentration in solution in
the zone of maximum bacterial growth. When these curves trended
upwards the residence time would be shorter, and when they trended
downwards the time would be longer. The goal was to achieve a
constant yield for better control of the system.

The duration of continuous experiments should be at least twice
the residence time of a discontinuous process, since the system
requires a time equal to the residence time to evacuate all metals
accumulated during the discontinuous stage. In fact it is during the
second stage that the system functions in continuous mode according
to the experimental conditions.
3.1. Preliminary test
The first continuous test was performed at 45 °C, with 20 days
residence time (across the three reactors) and without silver. The
variation of iron, copper and zinc in solution is shown in Fig. 2 .
The system achieved the highest yield in reactor R-1 during the
discontinuous stage, with dissolution of
26.6% Fe, 48.2% Cu and 44.4% Zn in the mineral.
Fig. 2. Preliminary test: 45 °C and 20 days residence time. Variations of the concentration
of iron (A), copper (B) and zinc (C).
However, the lowest metal concentration in solution was achieved in
the first reactor during the continuous stage. The dissolution of copper
and iron in reactor R-3 was practically double than in reactor R-2, and
in the latter it was double than in R-1. Such differences are to be
expected since there is an increase of metal concentration in solution
as the pulp passes through the reactors in cascade, so that the
mineral reaching each reactor is subject to heavier attack and hence
is free of surface products (flotation reagents, oxidized phases) which
can be harmful to bacterial activity. For that reason, the
microorganisms in reactor R-3 were supplied with a more readily
soluble substrate which substantially increased the dissolution yield.
 L. Cancho et al. / Hydrometallurgy 87 (2007) 100 – 111 105

and maintained the pH between 1.5 and 1 without acid addition,

through the regeneration of acid by bacteria. Only in the feeding tank
and in reactor R-1 were the values higher.

These results indicate that in spite of the long residence time

tested, the dissolution yield achieved was still low. The next step was
therefore to catalyse the process with silver.

3.2. Continuous bioleaching test with silver at 45 °C

A new continuous bioleaching experiment was performed at 45 °C

with 15 days residence time (across

Fig. 3. Preliminary test: 45 °C and 20 days residence time. Variations of the bacterial
population (A) and the redox potential (B).

Fig. 2 A shows the variation of iron in solution. The drop in

concentration caused by dilution at the outset of the continuous
process was followed by stabilization of the concentration after
approximately 10 days, which clearly indicates that the residence time
employed was appropriate for this metal. The lack of sharp
fluctuations in the concentration curve of this element is indicative of
weak precipitation of jarosites. Analysis of residues by X-ray
diffraction confirmed this point, since the proportion of jarosites was
small.

The variation of copper concentration ( Fig. 2 B)

reached a steady state later than iron, practically at the end of the
experiment, with copper dissolutions of 4 g/L. An overall copper yield
of 12% was achieved.
The dissolution rate of zinc remained practically unchanged
during both discontinuous and continuous stages, as sphalerite is the
most soluble mineral in the concentrate ( Fig. 2 C).

The bacterial concentration in solution during the continuous

experiment was stable, attaining high concentrations, above 10 8 cells/mL,
in all the reactors ( Fig. 3 A). Although there was also bacterial growth
in the feeding tank, the concentration was much lower than in the
reactors at all times. This bacterial activity raised the redox potential
Fig. 4. Continuous bioleaching with silver at 45 °C: 15 days residence time and 0.3 g
to 550 mV (vs. Ag/AgCl) ( Fig. 3 B) Ag/kg of concentrate. Variations of the concentration of iron (A), copper (B) and zinc (C).
106 L. Cancho et al. / Hydrometallurgy 87 (2007) 100 – 111

The copper dissolution rate increased in the three reactors during

the continuous stage, but the differences among them diminished. In
any case the overall dissolution yield of this metal was twice that
(24.5%) achieved in the test without silver ( Fig. 4 B). The zinc in
solution decreased, confirming that silver does not catalyse
dissolution of sphalerite, but conversely decreases its reactivity ( Fig.
4 C). The bacterial population was high, even more abundant than in
the test without silver, indicating that silver did not affect culture
growth and that the moderate thermophilic bacteria tolerated silver
well ( Fig. 5 A).

Fig. 5. Continuous bioleaching with silver at 45 °C: 15 days residence time and 0.3 g
Ag/kg of concentrate. Variations of the bacterial population (A) and the redox potential
(B).

the three reactors) using 0.3 g Ag/kg of concentrate, fixed on the

mineral surface at 35 °C for 24 h. This amount was chosen on the
basis of previous studies which demonstrated that lower amounts
were insufficient to catalyse chalcopyrite dissolution, whereas
amounts higher than 0.3 g Ag/kg of concentrate did not improve the
mineral dissolution ( Blázquez et al., 1999 ). In addition, these studies
showed that the most favourable temperature to fix silver on the
chalcopyrite surface was 35 °C ( Cancho et al., 2004 ). The results of
this test are shown in Fig. 4 . The

highest yield during the discontinuous stage was achieved in reactor

R-1 with dissolution of 34.8% Fe,
36.8% Cu and 71.8% Zn after 40 days. Silver was only added to the
feeding tank, and so the discontinuous stage prior to experiment 2
was performed under the same experimental conditions as the
previous test.
Based on the catalytic effect of silver ions on chalcopyrite
dissolution, it was decided to use a shorter residence time (15 days)
than in the preliminary experiment (20 days). Stabilization of the
system was readily achieved during the continuous stage, indicating
that the decision to shorten the residence time was the right one.
Fig. 6. Continuous bioleaching with silver at 40 °C: 0.3 g Ag/kg of concentrate and 15
days residence time. Variations of the concentration of iron (A), copper (B) and zinc (C).
 L. Cancho et al. / Hydrometallurgy 87 (2007) 100 – 111
Fig. 7. Continuous bioleaching with silver at 40 °C: 0.3 g Ag/kg of concentrate and 15
days residence time. Variations of the bacterial population (A) and the redox potential (B).
The redox potential in steady state was lower than in the absence
of silver. This is probably related to a decrease of the Fe (III)/Fe (II)
ratio produced by consumption of ferric ion during regeneration of the
catalyst according to reaction (2) ( Fig. 5 B).
3.3. Continuous bioleaching test with silver at 40 °C
Previous studies have shown that the catalytic effect of silver on
chalcopyrite is strongly affected by the temperature of fixation ( Blázquez
et al., 1999 ). For instance, dissolution of chalcopyrite increases
substantially at a silver deposition temperature of 35 °C but no
catalytic effect is observed at 68 °C. On the basis of these results, a
temperature of 40 °C, close to the optimum for the silver action (35
°C), was tested. A 5 °C reduction of temperature should not be as
detrimental to bacterial growth as exceeding the maximum growth
temperature; although it might affect the kinetics of the process, this
would be offset by silver catalysis. A third experiment was therefore
performed at 40 °C, maintaining a residence time of 15 days (across
the three reactors) with 0.3 g Ag/kg of concentrate fixed at 35 °C.
Fig. 6 shows the results of this test. The prior discontinuous stage
was also conducted in the presence
107
of silver. The highest yield was achieved in reactor R-2:
31.8% Fe, 48.6% Cu and 51.8% Zn, after 20 days. These results
indicated a higher rate of metal dissolution than in the corresponding
discontinuous stage of the previous experiment. This was possibly
due to the presence of silver, since in the previous experiment the
silver was not added during the discontinuous stage, but to the
feeding tank during the continuous stage.
During the continuous stage, a steady state of metal dissolution
was achieved half way through the experiment. A higher iron
concentration was reached, close to 6 g/L ( Fig. 6 A). However, copper
concentration decreased slightly with respect to the previous test ( Fig.
6 B). The overall copper yield was 18.4%, an intermediate value
between the two previous tests. The pH remained between
1.0 and 1.4 as in the previous tests. The most important differences
between this test and the one carried out at 45 °C were: a) an
increase in the amount of iron and zinc in solution, principally in the
last two reactors ( Fig. 6 A and C) and b) a decrease and stabilization
of copper dissolution; c) an increase of bacteria in suspension in all
the reactors, double that of the two previous tests ( Fig. 7 A); and d)
also high oxidizing potentials of 600 mV, mainly in the last reactors ( Fig.
7 B). Under these conditions, chalcopyrite passivation took place.
The increase in the redox potential and free bacteria in
suspension, with iron as the main oxidizable substrate, was probably
the result of selection of Feoxidizing bacteria in the culture caused by
a reduction in temperature. According to several authors ( Olson and
Clark, 2004; Third et al., 2002 ), Leptospirillum is the dominant species
in the bioleaching of gold concentrates at 40 °C and pH 1.6, with
arsenopyrite and pyrite as the main minerals.
Bacterial selection of this microorganism occurs when redox
potential is high because it is less sensitive to high concentrations of
ferric ion. The strong Fe-oxidizing tendency of Leptospirillum would
explain the high redox potentials attained during these experiments.
A 5 °C reduction in temperature modified the proportion of
Fe-oxidizing microorganisms in the mixed culture, raised the redox
potential of the solution to above 500 mV vs. Ag/AgCl causing
chalcopyrite passivation ( Third et al., 2002 ), and favoured the
dissolution of pyrite and sphalerite.
This temperature-dependant bacterial selection could negatively
affect the activity of S-oxidizing bacteria, which is inhibited in the
presence of high concentrations of ferric ion. These conditions
promote passivation of
108 L. Cancho et al. / Hydrometallurgy 87 (2007) 100 – 111

Fig. 8. Improved continuous bioleaching system. Variations of the concentration of iron (A), copper (B) and zinc (C).

the chalcopyrite surface and are unfavourable to its dissolution.
From these results it seems clear that the control of redox
potential is extremely important for the system, and this variable
would therefore be a good indicator of the effectiveness of
chalcopyrite catalysis.
3.4. Improved continuous bioleaching system
The last continuous bioleaching test was performed under the
best conditions established during the
previous experimentation: in an improved system at 45 °C. The main
changes introduced were:
a) The stirring rate was optimized to avoid settlement of the solid. The
use of a stirring rate in excess of 400 rpm during experimentation
produced a more homogeneous pulp, but this affected bacterial
growth negatively by increasing cell attrition and reducing the
adherence of microorganisms to the mineral, which is necessary
for oxidation of the sulphur that forms on the chalcopyrite surface.
A homogeneous
 L. Cancho et al. / Hydrometallurgy 87 (2007) 100 – 111
Fig. 9. Improved continuous bioleaching system. Variations of the bacterial population (A) and the redox potential (B).
pulp was achieved by improving the design of the reactors:
placing baffles in the walls, using a screw propeller capable of
generating greater turbulence, and supplying air from the centre
of the reactor bottom to give better gas distribution. As a result,
the solid was kept in suspension and mass transfer and optimum
conditions for the growth of bacteria were achieved.
b) The volume of the first reactor was doubled to increase the
residence time, considering that there is constant dilution in that
reactor due to continuous input of pulp.
c) The mineral was washed and silver was deposited on it at 35 °C to
eliminate surface compounds (flotation reagents and oxidation
products) that could interfere with the interaction between silver
and chalcopyrite.
d) Recent studies have shown that the growth ofmoderate
thermophilic microorganisms in continuous cultures and in the
presence of silver favours their S-oxidizing ability but inhibits their
Fe-oxidizing capability ( Cancho et al., 2005 ). However, the
presence of Feoxidizing microorganisms in the mixed culture is
important in order to regenerate the catalyst (reaction
109
(2)). The culture used in this experiment was a mixed one (Fe-
and S-oxidizing bacteria) of moderate thermophilic
microorganisms unadapted to silver.
During the test, different variables were modified to find the best
bioleaching conditions and to improve the overall yield of the process.
Fig. 8 shows the variation in the concentrations of iron, copper
and zinc during the experiment. A silver concentration of 0.3 g/kg of
concentrate was used during the discontinuous stage. The highest
dissolutions were achieved in reactor R-1: 42% Fe, 60% Cu and 53%
Zn. At the start of the continuous test, the concentration of catalyst
was kept at 0.3 g Ag/kg of RT and the residence time at 7 days.
The metallic dissolution decreased in all the reactors at the
beginning of the continuous process, indicating that the residence
time was too short to achieve stabilization of the system. Therefore, a
new residence time of 10.5 days was tried after day 60 of the test.
However, the system did not respond as expected. The redox
potential rose since the bacteria had longer to generate Fe (III), and
the feeding tank produced less
110 L. Cancho et al. / Hydrometallurgy 87 (2007) 100 – 111
dilution ( Fig. 9 B). This increase of the redox potential to above 500
mV in the three reactors coincided with a decrease of copper in
solution, which again confirms both the passivation of chalcopyrite at
high potentials and the absence of silver catalysis. The amount of
silver ion added could be insufficient if it partially reduces to metallic
silver. Increasing the residence time to 14 days (after day 77 of the
test) and the amount of silver to 1 g Ag/kg of RT (after day 100 of the
test) had a beneficial effect on the system: The redox potential
decreased and the copper dissolution increased. Once the system
stabilized, after 143 days, further silver was added (2 g Ag/kg of RT)
to improve the copper dissolution. After an initial reduction of copper
and iron in solution, both rose until the system stabilized. The drop in
metals seems to be connected with the culture's adaptation to the
increased amount of silver.
The increase of Zn in solution was associated with an increase of
the redox potential, leading to passivation of the chalcopyrite. The
consumption of Fe (III) during Zn dissolution produced a reduction of
the Fe (III)/Fe (II) ratio and hence of the redox potential, which again
favoured chalcopyrite dissolution.
The highest copper dissolution in the three reactors was achieved
with 2 g Ag/kg of concentrate, at a redox potential between 400 and
500 mV vs. Ag/AgCl and at a pH lower than 1.5. The last two
variables were responsible for the resulting stable and abundant
bacterial population ( Fig. 9 A), which indicates that in these conditions
silver catalysis was efficient. The conditions at the end of the
experiment were the best of all those tested: For the first time, the
system achieved a concentration of copper in solution of 11 g/L, with
an overall copper yield of 66%.
4. Conclusions
These experiments demonstrate the effectiveness of a mixed
culture of moderate thermophilic microorganisms and silver for
dissolution of chalcopyrite concentrates. The best results were
obtained with three tanks in series at 45 °C, a residence time of 14
days, a silver concentration of 2 g/kg of concentrate fixed on the
mineral surface at 35 °C, a stirring rate of 350 rpm, a pH between 1.2
and
1.4 and a redox potential between 400 and 500 mV. The continuous
bioleaching system produced copper solutions with concentrations
higher than 11 g/L and an overall copper yield of 66%.
Dissolution in the first reactor increased when the residence time
was doubled with respect to the other reactors, as microorganisms
were able to adapt better thanks to a constant supply of fresh pulp.
Silver substantially raised the rate of chalcopyrite dissolution and
copper extraction when the redox potential was lower than 500 mV
vs. Ag/AgCl.
Reducing the temperature caused selection of Feoxidizing
microorganisms and a consequent increase of the Fe (III)/Fe(II) ratio.
High Fe (III) concentrations inhibited the activity of S-oxidizing
bacteria and favoured passivation of chalcopyrite and dissolution of
pyrite and sphalerite.
The stirring rate was adjusted to optimize homogenization of the
pulp and the presence of microorganisms. A stirring rate higher than
350 rpm reduced the effectiveness of the culture due to increased cell
attrition and poorer adherence of microorganisms to the mineral,
which is necessary to oxidize the sulphur that forms on the
chalcopyrite surface.
Acknowledgements
The authors wish to express their gratitude to the Comisión
Interministerial de Ciencia y Tecnología (CICYT) of the Spanish
government for funding this work. Furthermore, one of the authors (L.
Cancho) wishes to express her gratitude to the Comunidad Autónoma
de Madrid for the graduate grant that helped her to carry out these
research studies.
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