A step closer to the leaching of

primary sulfides

The majority of copper sulfide reserves are found in the form of primary Guillermo Velarde. Sociedad Minera
Cerro Verde S.A .A ., Peru
sulfides, which may be processed by flotation followed by smelting/refining.
This metallurgical route is almost generally the preferred method to process
this type of ore. However, certain hydrometallurgical process can be less
expensive and potentially more amenable with the environment. Despite the
huge amount of research carried out over several decades on the leaching of
primary sulfides, to date, a viable technique has not been found to adequately
process marginal or below cut-off grades ores for concentrators. Currently,
copper is recovered with relative success from low-grade ores by bioleaching;
however, this depends on the pyrite content of the ore. The Cerro Verde mine
is well aware of the importance of temperature on the metal recovery process
and thus is focusing efforts to develop technology to raise heap temperatures
to well above normal levels using solar energy as a primary source of heat.
This approach can also be supplemented with the heat produced by the bio-
oxidation of pyrite. With the aid of solar energy, it will be possible to treat
minerals with low levels of pyrite and at the same time, obtain a higher and
much more uniform temperature over the leaching cycle. This paper present
several variables in terms of their effect on viability, including the quantitative,
linear influence of temperature on copper recovery, resulting in an increase
of around 2% for each Celsius degree. Pilot work has demostrated that heating
of the heap can be increased by 16°C in 40 days, using a solar-heated solution
at an irrigation flow rate of 17 l/h/m2.

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INTRODUCTION
It is widely accepted that temperature greatly affects chemical reactions and the kinetics of other
physical-chemical processes. It increases the velocity and/or levels of efficiency of many processes
and it especially affects copper leaching. According to our experiments, the kinetics and copper
recovery of primary mineral sulphides are much more sensitive to temperature than secondary
sulphides. A higher temperature influences the process chemistry; mass transfer and both the
quantity and type of the bacterial population and activity (Velasquez et al., 2012 & Demergasso et
al., 2012).
Likewise, it is well-known that the leaching of primary sulphide minerals is an extremely slow
process with very low rates of recovery at atmospheric temperature and pressure. Therefore, until
now, leaching is only feasible with low-grade minerals with no size reduction (ROM), or only after
the ore has been processed through primary crushing in a marginal operation, such is the case of
the Toquepala Dump Leach Operation in southern Peru. If the pyrite content of the mineral is high,
this process is more likely to be successful (e.g. at Toquepala, the pyrite content of the low grade
primary sulphide is in the order of 5 to 8%). The heat, generated mainly by the bio-oxidation of
pyrite, raises the temperature of the heap or stockpile, which in turn increases copper recovery and
produces sulphuric acid as well.
Thus, the pyrite content of the mineral has a direct impact on the kinetics of copper recovery.
Nevertheless, it is difficult to control the kinetics of oxidation of the pyrite sufficiently to reach and
maintain the desired temperatures for long enough to significantly impact recovery. Therefore, by
itself, this process is not efficient enough to be used in the leaching of primary sulphides (Velarde,
2013 & Demergasso et al., 2012).
This paper summarises experiments carried out into heap leaching, solar heating and the irrigation
of a leaching heap. The relationship of the recovery of sulphides of copper to temperature is
investigated. An example shows how the temperature of the heap can be increased by almost 20
Celsius degrees using solar heating. Solar heating of leaching solutions has shown being more
effective than the practice of covering heaps with transparent films which only provides a delta in
temperature between 3 and 6 Celsius degrees depending on climatic conditions (Servicios
Asociados, 1999, & Velarde, 2002)
The higher process temperature, obtained with the aid of solar heating, improves pyrite oxidation
kinetics. In turn, the heat generated from oxidation helps off-set deficiencies in solar heating during
cloudy days and low ambient temperature moments of the day or the year. Therefore, the
combination of solar heating and pyrite oxidation can make the leaching of primary sulphides more
viable than ever.

THE EFFECT OF TEMPERATURE ON THE KINETICS OF COPPER RECOVERY:

RESULTS AND DISCUSSION

Secondary sulphides
Figure # 1 shows copper recovery over time curves for secondary sulphide leach column tests
performed at four different temperatures at the same grain size gradation corresponding to a P80 of

112
10 mm. The directly proportional relationship between temperature and copper recovery can be
clearly seen after the first 37 days of leaching. Likewise, Figure # 2 shows that this relationship is
linear over the leaching period. It can also be seen that the higher the temperatures, the lower the
delta copper recoveries are. Furthermore, Figure # 3 shows how delta copper recovery drops with
leach time due to increased temperature (35 °C compared to 20 °C). The mineral sample tested had
1.04% of total copper, 0.21% acid soluble copper, 0.55% cyanide soluble copper, and a leaching
index or solubility ratio of 0.731. This plot can be used for scale-up purposes, since normally
ambient temperature column leach tests are easier to run than heated column tests.

Figure 1 The effect of temperature on the recovery of secondary sulphide copper minerals

Figure 2 The linear effect on recovery Figure 3 The fall in delta of recovery achieved
by leaching at 35 °C compared to 20 °C

Primary sulphides
Figure # 4 shows the recovery curves obtained during leaching tests in columns with low-grade
primary copper sulphide with a grain size at a P80 of 10 mm. The columns were run at an
approximate ambient temperature of 37 °C. The ore characteristics were: 0.231% total copper,

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0.011% acid soluble copper, 0.011% cyanide soluble copper soluble, and a leaching or solubility
index of 0.095; the pyrite content was 1.5% and the proportion of chalcopyrite compared to the total
copper minerals present in the sample was 97.5%.
After 850 leaching days, the higher process temperature resulted in a recovery of 60%, compared to
20% for the ambient temperature process. While the curves continued to be divergent, with the
higher temperature process continuing its upward trend, these results were very different from
those obtained with secondary sulphides, where the impact of temperature is lower and decreasing
over time.
Figure # 5, shows that the relationship of recovery to temperature remained linear after 220 days of
leaching at around 60 °C. In this case, two points were obtained from the above mentioned tests run
at Cerro Verde, while the rest of the time-recovery points of the curve were obtained from tests run
at the Phelps Dodge Mining Technology Center (Uhrie, 2004). The increase in delta recovery due to
temperature is shown on Figure # 6.

Figure 4 The effect of temperature on the recovery of primary sulphide copper minerals

Figure 5 Linear effect of temperature over Figure 6 Delta recovery increase over time

recovery after 220 days of leaching

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HEATING OF LEACHING HEAPS

State of the art

Some sulphide leach operations, especially those located at high altitude, cover the heap with a
transparent plastic film to achieve temperature gains ranging from 3 °C to 6 °C, depending on
ambient conditions. In this case the operational strategy is more oriented to reduce the heap cooling
rather than increase the temperature inside the heap.
Other operations, such as Quebrada Blanca in Chile, take advantage of the residual heat of their
electricity generators to warm up the air being blown into the heaps.
There is also a patented process to heat heaps, using Fresnel lenses or parabolic mirrors, to heat a
thermal fluid to 150 °C, which in turn heats the leach solutions, some of which can even be stored to
be used for night-time irrigation (Hernandez, J. O & Casas de Prada, J. M., 2012).
The high temperatures achieved inside leach dumps of low copper grade primary ores are basically
the result of heat generated by the oxidation of their relatively high pyrite contents. Nevertheless,
this process is difficult to control, since normally at the beginning, the mass of pyrite quickly reacts
and oxidizes producing large quantities of heat, which are lost to the environment mainly by
convection; then, the temperature inside the heap drops at a time when there are copper quantities
yet to be extracted.

Project concept
The project involves the placing of pipes in a serpentine formation, covered with transparent plastic
sheets, in a permanent installation outside the heap. The system is used to capture solar energy and
heat the leach solutions, which flow through the pipes, just like solar-water heaters. Then, the
heated solution is conveyed to the drip irrigation lines installed at the surface of the heap, which is
also covered with transparent plastic sheets to avoid evaporation, reduce heat loss and allow solar
radiation to act over the heap surface. One of the main objectives was to use an economical material
for the pipes, which would result in a simple, cheap and effective system.
Initially, the pilot plant only supplied hot leach solution during sunny periods, 8 hours per day.
Later on, during the second stage of the tests, storage tanks were used to allow irrigation of the
heap over non-sunny periods. The irrigation flow rate during the heating stage was high, 17 l/h/m2,
to compensate for the lack of irrigation at night and to heat the heap as quickly as possible. This
also meant that the equilibrium temperature could be reached sooner.
The irrigation regime should follow the kinetics of the leaching of copper-sulphides process, which
is initially high and later begins to decrease; that is, there should be a high initial flow rate to meet
the preliminary heating requirements of the heap, followed by a reduced flow rate to continue
leaching and maintain the equilibrium temperature of the heap. Nevertheless, every operation is
unique; for example, in the case of a permanent pad with interconnected layers, the lower layers,
which work at ambient temperature, have to be heated to be able to achieve delta copper recoveries,
especially if high-refractory minerals are present.

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PILOT PLANT TEST

Description
After promising, initial small-scale testing of irrigation with heated solutions, a higher-scale
definitive pilot test was carried out, the main characteristics and results are shown in Table 1.

Table 1 Main characteristics of pilot test

Item Magnitude

Heated area 750 m2

Test mineral 5,100 mt

Total length of heating pipe 25,000 m

Irrigation area 441 m2

Flow rate of heated solution 125 l/min (33 gpm)

Irrigation flow rate 17 l/h/m2

Evaluated depth of heap 7.0 m

Average solution temperature during the sunny

60 °C
period at the heating system outlet in Summer.

Average solution temperature during the sunny

46 °C
period at the heating system outlet in Winter.

The heating of a serpentine pipe

Tests prior to the pilot test allowed the determination of the optimum length of serpentine for a
specific solution flow rate, to be determined. Figure # 7 shows the curves of temperature increase
with length of serpentine at different times of a sunny day. Figure # 8 shows the curve of average
temperature achieved versus length of pipe over said period.
80
70
70
60
60
50
50
Temperature (°C)
Temperature (°C)

40 40

30 30

20 20

10
10
0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180
Pipe Length (m)
8:00 a 9:00 7:35 a 8:00 11:00 a 12:00 12:00 a 13:00 13:00 a 14:00 15:00 a 16:10 Adjusted curve Real Data Pipe Length of heating (m)

Figure 7 Temperature increase over the length of Figure 8 Average temperature increase over
heating pipe for a given solution flow at the length of heating pipe for a given
different times of day solution flow rate on a sunny day

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Heat loss
The heat loss from the surface of the heap to the environment during a sun-free period, as expected,
falls as depth increases, reaching zero at 50 cm. The external perimeter of the leached section also
loses heat towards the surrounding mineral, which greatly affects its temperature. However, the
test demonstrated that it had almost no effect on the centre of the heap (at 10.5 meters). These heap
boundary losses are, as could be expected, relatively unimportant for the system as a whole,
provided the heated leaching area is large. Figure # 9 shows the curves of temperature at different
depths, determined at around 4:00pm one day, and at 8:30am on the following day:
50

45
45 43
41
40
40 39
Temperature (°C)

38 37

35 36
35 37
34
30 32
30
28
25
16.47 12.39 9.00 5.59 3.56 1.09 0.00
Temperature Delta
20
5 10 20 30 40 50 60
Temp. Morning following day Temp. Afternoon day 1 Thermometer Depth (cm)

Figure 9 Cooling of heap during sun-free period

Thermal balance
The final objective of the test was to obtain the thermal balance of the heap being heated. The
results obtained are shown on Figure # 10. The curve of speed of heating is adjusted to fit the real,
actual data. The curve of losses to the ambient is based on calculations made from one day to the
next, over the sun-free period. The other curves were also calculated using experimental data of
balanced system temperatures.

45 2400000

40 2100000

35 1800000

30 1500000
Temperature (°C)

Heat (Kcal/day)

25 1200000

20 900000

15 600000

10 300000

5 0
0 5 10 15 20 25 30 35 40 45 50
Leaching Time (days)
Temperature reached Gross heat applied to system
Net Heat required to achieve a daily increase of temperature Heat not used to increase the temperature of the heap
Total heat loss non-sunny period from 0 to 60 cm

Figure 10 Thermal balance of heap

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Economics of project
The total unit cost of heating the solution to 53 °C at the heating system outlet to achieve a delta of
32 °C, and taking into account winter/summer average temperature and the average temperature of
a sunny day, was 0.195 $/m3 with an additional cost to cover the surface of the heap of 1.37 $/m2.

CONCLUSIONS
The oxidation of chalcopyrite, the most refractory of the leaching minerals, is heavily influenced by
the process temperature. Thus, primary sulphides are much more sensitive to temperature than
secondary sulphides. Therefore, additional heating combined with the heat provided by the
oxidation of pyrite, could improve the leaching of primary sulphides in the dump or heap
The success of leaching at above normal temperatures using solar energy, depends on the
application of new irrigation concepts, the level of solar radiation, the climate, and the
characteristics of the mineral to be processed.
The heating system tested increased the temperature of the heap by an average of up to 37 °C,
with a temperature delta of 16 °C during 40 summer days. The average depth of the heap was 7 m.
The total solar-heated irrigation system unit cost was 0.195 US$/m3 of heated solution plus 1.37
US$/m2 of heap area subjected to irrigation.

ACKNOWLEDGEMENTS
The author wishes to thank Javier E. Guevara, Manager of Hydrometallurgical Processes of
Sociedad Minera Cerro Verde, for supporting this project and its presentation at Hydroprocess
2013.

REFERENCES
Uhrie, L. John, (2004) Effect of Temperature and Bacterial Population on Pyrite and Chalcopyrite Leaching,
Process Technology Center of Phelps Dodge Mining Company, Arizona, USA.

Hernandez, J. O & Casas de Prada, J. M. (2012) Process and System for Solar Leaching Cells Using Solar
Concentrating Collectors Based on Fresnel Lens with Solar tracking.
http://ip.com/patfam/es/46639000#desc.

Demergasso, C., Iturriaga, V., Galleguillos, P., Acosta, M., & Soto, P.. Espoz Ch., Velasquez A. & Pinilla C.
(2012) A Shift from Mesophilic to Moderate Thermophilic Populations in an Industrial Operation of a
Heap Bioleaching Process, Minera Escondida, Universidad Católica del Norte and CICITEM, paper
published at Hydroprocess 2012, Chile.

Velasquez, A., Sutherland, F., Espoz Ch. & Pinilla C. (2012) Evolution of the Microbial Consortium through
Leaching Cycles in Minera Escondida, paper published at Hydroprocess 2012, Chile.

Servicios Asociados (1999) Aumento de temperatura en las pilas de lixiviación y el efecto del film Therm-2,
Chile.

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