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Effect of morphology on sulphuric acid leaching of malachite ores

Article  in  Mineral Processing and Extractive Metallurgy IMM Transactions section C · May 2011
DOI: 10.1179/1743285510Y.0000000008

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Effect of morphology on sulphuric acid
leaching of malachite ores
S. Song*1,2, F. Rao2 and X. Zhang2
The relationship between copper leaching from malachite ores by using sulphuric acid as the
lixiviant and the morphology of malachite particles associated with the gangue minerals has been
studied in this work by means of scanning electron microscope. This study was performed on two
malachite ores that are associated with the gangue minerals in the forms of thin films and
granules. The experimental results have shown that the leach kinetics closely correlated with the
morphology of malachite in the ores. Owing to the larger specific surface area, the thin film
malachite had a much higher copper leaching rate than the granular malachite. As a result, a
higher copper recovery could be achieved from the thin film malachite.
Keywords: Copper leaching, SEM, Morphology

Introduction
In the past decade, copper production contributed
through hydrometallurgical technology has steadily
increased, from 2% of the total copper mine production
in 1980 to more than 20% in 2006.1 This technology
includes leaching with sulphuric acid, solid–liquid separa-
tion, solvent extraction and electrowinning.2,3 Because of
low cost, short construction time, operational simplicity,
good performance and environmental advantages, it has
proved to be a successful method for the recovery of
copper, particularly from low grade ore bodies.4,5
Fundamentally, the development of a copper leaching
process involves three phases: testing, engineering design
and operations. In the testing, the mineralogical
characterisation of the leached copper ores plays an
important role in determining the leaching rate curve for
copper dissolution and a corresponding rate curve for
acid consumption.6 It includes the ore type (oxide and
sulphides), the copper grade, the gangue minerals in the
ores, the disseminated size of copper minerals, etc. There
are numerous reports on the leaching of copper from
chalcopyrite ore.7,8 However, few researchers have
investigated the effect of the morphology of copper
minerals disseminated in gangue minerals on copper
leaching from ores.
The objective of this study was to obtain a better
understanding of the extraction of copper from ores
through the sulphuric acid leach of two types of
malachite ores (one with malachite disseminated in the
gangue minerals in the form of thin films and the other
as granules) using scanning electron microscopy (SEM)
to characterise the morphology.
1
Faculty of Resources and Environmental Engineering, Wuhan University
of Technology, Luoshi Road 122, Wuhan 430070, China
2
Instituto de Metalurgia, Universidad Autónoma de San Luis Potosı́, Av.
Sierra Leona 550, San Luis Potosı́, C.P. 78210, Mexico
*Corresponding author, email shaoxian@uaslp.mx
Experimental
Materials
Two copper oxide (malachite) ore samples used in this
work were collected from the Northcopper mine located
in Coahuila state and the Lupe mine located in Puebla
state, Mexico respectively. Both samples were crushed to
100% minus 1 cm by passing through laboratory scale
jaw and cone crushers. The chemical analysis results of
the ore samples are given in Table 1. The mineralogical
compositions of the ore samples are given in Table 2, in
which the contents of the main gangue minerals are
included.
The sulphuric acid used in this work was from
Productos Quimicos Monterrey Ltd. The water used in
this work was the tap water in San Luis Potosi City.
Agitation leach test
One kilogram of the crushed samples was mixed with
550 mL of water and ground to 56% minus 74 mm with a
laboratory scale rod mill. Then, the ore slurry was
transferred into a 2000 mL cylindrical glass reactor with a
height of 18 cm and an inner diameter of 14?5 cm, and
was diluted to 34% solids by the addition of dilute
sulphuric acid solution. The acid concentration was
adjusted to achieve a range of specific acid addition from
25 to 300 kg t21. A Cole–Parmer mixer was applied to
agitate the ore suspension at 500 rev min21 during the
leach test for 4 h. The ore slurry was filtered to separate
the leachate and the leach residue. The leachate was
assayed for Cu by chemical analysis using atomic
absorption spectroscopy. The residue was dried, weighed
and then assayed for copper. The copper recovery of the
leach R (%) was calculated from the expression
Wl
R~ |100% (1)
Wl zWr
where Wl and Wr are the weights of copper in the leachate
and the leach residue respectively.

ß 2011 Institute of Materials, Minerals and Mining and The AusIMM

Published by Maney on behalf of the Institute and The AusIMM
Received 20 May 2010; accepted 25 November 2010 Mineral Processing and Extractive
DOI 10.1179/1743285510Y.0000000008 Metallurgy (Trans. Inst. Min Metall. C) 2011 VOL 120 NO 2 85
Song et al. Effect of morphology on sulphuric acid leaching of malachite ores

1 Images (SEM) of Northcopper ore

2 Images (SEM) of Lupe ore

Column leach test
A cylindrical column of 1?5 m height and 10 cm inner
diameter was used for the column leach test. A known
mass of crushed ore (100% passing 1 cm screen) was first
wetted with water and then packed into the column.
Next, dilute sulphuric acid solution (2?5%, v/v) was
added to the column until all the particles were
immersed. After 24 h, the leachate was drained from
the column bottom, measured for volume and assayed
for copper. Sequentially, fresh dilute sulphuric acid
solution was again added to the column and removed
after another 24 h. This cycle was repeated for several
days until the terminal liquor concentration was
,0?25 g L21 Cu. The copper recovery of the leach R
(%) was calculated from the expression
Wl
R~ |100%
Wf
where Wl and Wf are the weights of copper in the
leachate and the feed respectively.
SEM measurement
A Philips XL30 field emission gun SEM was used to
observe the form, size and association of copper and
gangue minerals in the ore and leach residue samples.
The mineral composition was characterised by the atta-
ched energy dispersive X-ray spectroscopy (EDX).
Results and discussion
Morphology of the malachite ores
The morphology of malachite particles in the
Northcopper and Lupe ores was studied using SEM
and EDX. The results are shown in Figs. 1 and 2. The
malachite in the Northcopper ore appears on the gangue
minerals (silicate minerals and calcite) in the form of
thin films (Fig. 1). The thickness of the films is ,1 mm.
This morphology might originate from the spreading of
malachite coulees into the gangue minerals during the
formation of the ore. When the ore is crushed and
ground, it breaks up along the interface of malachite and
(2) gangue minerals, producing malachite coated gangue
particles in the form of thin films. Obviously, it is very
hard to completely liberate the malachite in the
Northcopper ore.
However, a study of the morphology of the malachite
particles in the Lupe ore shows that the malachite
particles are associated with the gangue minerals in the
form of granules (Fig. 2). During the formation of
malachite particles, the Lupe malachite developed in

Table 1 Chemical analysis of the Northcopper and Lupe ore samples

Sample Au/g t21 Ag/g t21 Cu/% Zn/% Pb/% Fe/% Mn/% CaO/% S/% Insoluble/%

Northcopper 0.06 9 2.16 0.19 0.07 0.9 0.85 1.42 2.3 89

Lupe 4 15 1.4 0.05 0.1 10.4 0.06 8.6 2.8 44.4

86 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2011 VOL 120 NO 2

3 Copper leach recovery from Northcopper and Lupe
ores as function of sulphuric acid dosage after 60 min
of agitation leach
4 Copper leach kinetics from Northcopper and Lupe ores
with 4 h agitation leach
three dimensions, whereas the Northcopper malachite
developed in two dimensions. Clearly, the Northcopper
malachite has a much larger phase specific surface area
than the Lupe malachite.
Leaching of the copper ores
The copper recoveries from the two ores after 60 min in
the 4 h agitation leach tests as a function of sulphuric
acid dosage are shown in Fig. 3. The copper recovery
from the Northcopper ore sharply increased with
increasing sulphuric acid dosage and reached a plateau
at 95% at a dosage of 92 kg t21. In the case of the Lupe
ore, the increase in copper recovery was sharp in the
dosage range of 0–50 kg t21 and then tapered off. The
recovery reached y63% at a dosage of 300 kg t21.
Figure 4 illustrates the agitation leach kinetics of
copper from the two ores at a sulphuric acid dosage of
Table 2 Mineralogical compositions of the Northcopper ore and Lupe ore samples (%)
Sample Malachite Limonite
Northcopper 3.76 1.31
Lupe 2.44 14.44
Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)
Song et al. Effect of morphology on sulphuric acid leaching of malachite ores
5 Copper leach kinetics from Northcopper and Lupe ores
with column leach
92 kg t21. The copper recovery from the Northcopper
ore dramatically increased and reached 95% at 60 min
and then slightly increased to 98% at 240 min. In the
case of the Lupe ore, the copper recovery was y52% at
60 min and 81% at 240 min respectively. It is clear that
the leaching rate and efficiency of copper extraction
from the Northcopper ore are much higher than those
from the Lupe ore.
The agitation leach results of the Northcopper ore
were in very good agreement with those presented in
many literatures on malachite ore leach study.9–11 For
instance, Bingola and Canbazoglu reported that 94%
copper recovery has been achieved from sulphuric acid
leaching of a malachite ore at 25uC after 180 min
leaching;9 in the solutions of inorganic acids (H2SO4,
HCl and HNO3), copper dissolution from copper oxide
ores could reach 99?95% at 25uC.10
Column leach with sulphuric acid as the lixiviant was
also tested on coarse particles (100% minus 1 cm) of the
two copper ores. Figure 5 shows the cumulative copper
recovery from the two ores in the column leach tests as a
function of leaching time. The tests were carried out at a
column height of 1?5 m. The cumulative copper recovery
increased with increasing leaching time and reached a
plateau after 10 days for the Northcopper ore (98%
recovery). After 14 days for the Lupe ore, the recovery
was 78% and was still increasing slowly. These results
indicate that the column leach of copper from the
Northcopper ore is much more efficient and faster than
that from the Lupe ore. These observations are in good
agreement with the results from the agitation leach test
plotted in Fig. 4.
Effect of malachite morphology in copper
leaching
As already stated, the leaching of malachite in a
sulphuric acid solution is a chemical process, which
can be represented by following reaction
Pyrite Limestone Silicate Sphelarite
0.32 2.54 89.0 0.28
4.32 15.34 66.35 0.07
2011 VOL 120 NO 2 87
Song et al. Effect of morphology on sulphuric acid leaching of malachite ores
6 Images (SEM) of Northcopper after being leached
CuO(s) zH2 SO4(aa) ?CuSO4(aa) zH2 O
Therefore, the dissolution of malachite would leave
holes or dishes on the gangue mineral surfaces of the
same size as the malachite before leaching. As shown by
SEM images in Fig. 6, the malachite films on the
Northcopper ore were completely leached out, leaving
many very shallow dishes on the silicate mineral
surfaces. However, there were many holes and gullies
on the Lupe ore after being leached, as shown in Fig. 7.
The size of the holes was about 4–20 mm, and the length
of the gullies was about 20–50 mm. The formation of
shallow dishes on the Northcopper ore was due to the
leaching out of the thin films of malachite, and the
formation of the holes and gullies on the Lupe ore was
attributed to the leaching out of the granular malachite.
As shown in Figs. 4 and 5, the Northcopper ores
responded to sulphuric acid leach much more rapidly
than the Lupe ore, although the two ores had similar
copper mineralisation. This observation might be
attributed to the different morphologies of the malachite
particles in the two ores. The thin films of malachite
particles on the Northcopper ore had a much larger
specific surface area than the granular malachite
particles on the Lupe ore. A larger specific malachite
surface area leads to more contact of malachite with
sulphuric acid solution. This contact is a key point for
the chemical reaction. The greater the contact surface,
the higher the leaching rate. Accordingly, the morphol-
ogy of malachite association with gangue minerals is
shown to be an important factor in the leaching of
copper ores.
7 Images (SEM) of Lupe ores after being leached
88 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)
From the viewpoint of ore fragmentation, it is easier
to expose malachite surfaces from a thin film malachite
ore than from a granular malachite ore, because of the
larger phase specific surface area and the preferential
breakage. In contrast, there might be a significant
portion of malachite grains fully entrapped by the
gangue minerals after a granular malachite ore is
fragmented. With a lack of access for the lixiviant, the
entrapped malachite could not be leached out, leading to
a lower copper recovery for the granular malachite ore.
This would account for the lower copper recovery
achieved from leaching the Lupe ore.
It is worth noting that acid leach of copper from
malachite ores is also affected by the presence of gangue
minerals in the ores, such as acid consuming minerals
and clay minerals.12 In this study, the Lupe ore
contained much more acid consuming gangue minerals
than the Northcopper ore, 14?4% versus 1?3% limonite,
4?3% versus 0?3% pyrite and 15?3% versus 2?5% lime-
stone (Table 2). The higher grades of the acid consum-
ing gangue minerals in the Lupe ore not only consumed
more sulphuric acid, but also reduced the leach rate of
copper, which might be another mechanism for a higher
leaching rate being achieved with the Northcopper ore
than the Lupe ore.
Conclusion
1. The experimental results presented in this work
have shown that in the leaching of copper from
malachite ores, there is a close correlation between the
leaching rate of copper and the morphology of the
2011 VOL 120 NO 2

malachite mineralisation in its association with the
gangue minerals in the ores. A much higher leaching
rate was achieved from a thin film malachite ore than a
granular malachite ore. This is believed to be due to the
fact that the thin film malachite has a much larger phase
specific surface area and thus a more contact surface
with the sulphuric acid, leading to a more rapid chemical
reaction.
2. A higher copper recovery was obtained from the
thin film malachite ore than the granular malachite ore
probably due to a lack of access of the leachant to some
malachite grain in the granular ore.
Acknowledgements
The financial supports for this work from the Consejo
Nacional de Ciencia y Tecnologı́a (CONACyT) of
Mexico under grant nos. 48436-Y and 92506 are grate-
fully acknowledged. In addition, F. Rao would like to
thank CONACyT for offering him a scholarship under
grant no. 213624 while studying for his PhD degree.
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