Hydrometallurgy 72 (2004) 159 165

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Dissolution kinetics of malachite in sulphuric acid

D. Bingol a, M. Canbazoglu b,*
a

Department of Mining Engineering, Dumlupnar University, Kutahya, Turkey

b
Department of Mining Engineering, Cumhuriyet University, Sivas, Turkey

Received 28 May 2003; received in revised form 1 October 2003; accepted 5 October 2003

Abstract
A kinetic study of the sulphuric acid leaching of oxidised copper ore, primarily malachite, was carried out. The effects of
leaching time, stirring speed, acid concentration, solid to liquid ratio, reaction temperature, and particle size of the ore were
investigated. Using the best conditions, the copper recovery was nearly 94% at 25 jC and 99% at 80 jC after 180 min leaching.
Dissolution of malachite during the leaching was described by a logarithmic function, y = a ln(x) + b. The data obtained for the
leaching kinetics indicated that the initial dissolution of malachite is a diffusion controlled reaction.
D 2003 Elsevier B.V. All rights reserved.
Keywords: Malachite; Dissolution; Copper; Sulphuric acid; Leaching; Kinetics

1. Introduction
Copper was the first metal to which hydrometallurgical processes including leaching, solvent extraction and electrowinning (L-SX-EW) were applied
(Seward, 1997, 1999; Hopkins, 1994). During the
leaching of copper minerals, such as chalcopyrite
(CuFeS2) or tenorite (CuO), sulphuric acid and ammonia are generally the most used leaching mediums
(Bingol et al., 1994; Amores et al., 1997; Navarro and
Alguacil, 1999; Alguacil, 1999). Copper oxide minerals contain copper in the divalent state (e.g. azurite
(Cu3(OH)2(CO3)2), malachite (Cu2(OH)2CO3), tenorite (CuO) and chrysocolla (CuSiO3.2H2O)), and these
are completely soluble in sulphuric acid at room

* Corresponding author.
E-mail address: mcanbaz@cumhuriyet.edu.tr (M. Canbazoglu).
0304-386X/$ - see front matter D 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2003.10.002

temperature. Typical reactions of oxidised copper ores

with sulphuric acid can be given as follows (Blazy,
1970; Barlett, 1992),
Cu3 OH2 CO3 2 3H2 SO4
! 3CuSO4 2CO2 4H2 O

Cu2 OH2 CO3 2H2 SO4 ! 2CuSO4 CO2 3H2 O

2
CuO H2 SO4 ! CuSO4 H2 O

CuSiO3 :2H2 O H2 SO4 ! CuSO4 SiO2 3H2 O

4
The cost of acid may be the most important
economic factor in the leaching of oxidised copper
ores. Carbonate rocks, such as limestone and dolo-

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D. Bingol, M. Canbazoglu / Hydrometallurgy 72 (2004) 159165

mite, are often significantly found in the ores and

consume additional acid according to the reaction
given below (Blazy, 1970; Barlett, 1992):
CaCO3 H2 SO4 H2 O ! CaSO4 :2H2 O CO2
5
To determine the leaching parameters, the dissolution of malachite in sulphuric acid solutions has been
recently studied by the Taguchi method (Ata et al.,
2001). In this study, the kinetics of malachite leaching
was not evaluated and the optimum leaching conditions were determined as: temperature, 40 jC; solid to
liquid ratio, 0.1 g cm 3; sulphuric acid concentration,
10%; reaction time, 45 min; particle size, 10 mesh and
stirring speed, 480 rpm. Under these optimum working conditions, the recoveries of copper and iron from
malachite ore were 100% and 58%, respectively.
The aim of this present study is to determine and
discuss the dissolution kinetics of malachite in sulphuric acid. For this purpose, the initial dissolution
rate and activation energy were determined and the
effect of other minerals on leaching reactions were
taken into the consideration.

and the sulphur from the base metal minerals. Quartz

was determined using the conventional hydrofluoric
acid method. The ore was first crushed, ground and
then screened to obtain the desired particle size
fractions for the leaching experiments.
The leaching experiments were performed in a 600
mL Pyrex beaker in a thermostatically controlled
water bath, and equipped with a thermometer and
Teflon stirrer agitated mechanically. The ground copper ore was added into the agitated sulphuric acid
solution at the required temperature. After pre-determined time intervals, 5 mL of leaching solution
sample was withdrawn from the reactor and 5 mL
of fresh sulphuric acid solution was added immediately to leaching medium. After filtration, the clear
leach solution sample was analysed for copper by
AAS. The weight loss during leaching was calculated
by difference. The acid consumption was determined
by titration of the leach solution with NaOH, using
dimethyl yellow + methylene blue as indicators. For
the leaching experiments where the acid concentration
and solid to liquid ratio were examined, the ore
sample has a P80 of 0.65 mm was used, the 100
150 Am size fraction was used to test the effect of
temperature.

2. Experimental
3. Results
Oxidised copper ore was used for the leaching
experiments. Mineralogical analysis, performed using
a Rigaku DMAX IIIC model X-ray diffractometer
using CuKa radiation at 35 kV and 15 mA, indicated
that malachite, pyroxene group minerals, quartz, goethite and magnetite were the major mineral phases in
the ore. The chemical analysis of the malachite ore
sample is presented in Table 1. Copper, iron, nickel,
cobalt and chrome value were determined by using
Atomic Absorption Spectrophotometer (AAS). Sulphur and carbon content were determined by using
LECO-444 SC analyser. The carbon in the ore originates from carbonate content of malachite mineral,

3.1. Effect of leaching time

The effect of leaching time on the dissolution of
malachite is shown in Fig. 1. Clearly, the copper
recovery increased with increasing leaching time with
the initial dissolution of copper being very rapid.
After 5 min, 77% copper recovery was achieved and
this increased to 97% after 210 min. In practice, 30
min of leaching time was found to be optimum. It is
clear that chemical reaction of malachite with sulphuric acid determines the dissolution rate of malachite
during the leaching.
3.2. Effect of sulphuric acid concentration

Table 1
Chemical analysis of ore
Component (%)
Cu

Fe

Ni

Co

Cr

SiO2

28.36

15.74

0.044

0.010

0.019

0.10

2.72

15.34

The effect of sulphuric acid concentration on the

dissolution of malachite was investigated. The copper
recovery, acid consumption and weight loss are given
in Fig. 2. It can be seen that there is a direct

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161

3.3. Effect of stirring speed

Fig. 3 shows that stirring speed has a significant
effect on the dissolution of malachite. The copper
recovery obtained under the same experimental conditions without agitation was 39%, while it was nearly
87% when 170 350 rpm stirring speed was applied.
The same effect of stirring speed was observed on the
dissolution of the iron minerals. There was no apparent iron dissolution in the absence of agitation, but it
was 21% at 300 rpm. It can be concluded that this
effect occurs by the increased diffusion rate of ions in
leaching medium with increasing agitation.
3.4. Effect of solid/liquid ratio

Fig. 1. The effect of leaching time on the recovery of copper from

the malachite ore (acid concentration, 2.04 mol/L; temperature, 25
jC; particle size, 80%  650 Am; the amount of ore, 20 g; solid to
liquid ratio, 1:5 g/mL; stirring speed, 250 rpm).

relationship between the copper recovery and the acid

consumption. The consumption was high until 1.02
mol/L sulphuric acid was used, e.g. the copper recovery was 87% and the acid consumption was about
85% when 1.02 mol/L sulphuric acid was used. Acid
in the leaching solution (97%) was consumed while
0.61 mol/L sulphuric acid was used and the copper
recovery was approximately 57%.
For the acid concentrations higher than 1.02 mol/L,
both acid consumption and copper dissolution rate
decreased. When 2.04 mol/L of sulphuric acid was
used, the acid consumption was 20% and the copper
recovery remained 91%. The weight loss increased
with acid concentration and reached 48% when 2.04
mol/L of sulphuric acid was used. It was found that
this value was also equivalent to the malachite dissolution from the sample.
The experimental results showed that the acid
consumption was 0.92 mol/L for 90% copper recovery. From reaction (2), the theoretical amount of acid
consumed during leaching can be calculated. Under
the experimental conditions, 0.80 mol/L acid is required for malachite dissolution. It is suggested that
the slightly higher value in practice is due to acid
consumption by gangue minerals.

Fig. 4 gives the copper recovery and the weight loss

that occurred during leaching, as the function of the
solid to liquid ratio (weight of solid/volume of liquid).
According to experimental results presented in Fig. 4,
it was found that the copper recovery increased until
the solid/liquid ratio was 1:5, where 87% of copper
was recovered. At ratios higher than 1:5, there was no
significant increase in the copper recovery. During the

Fig. 2. Effect of sulphuric acid concentration on the recovery of

copper from the malachite ore, and on the acid consumption and the
weight loss during the leaching (temperature, 25 jC; particle size,
80%  650 Am; the amount of ore, 20 g; solid to liquid ratio, 1:5 g/
mL; stirring speed, 250 rpm; time, 30 min).

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Fig. 3. Effect of the stirring speed on the recovery of copper and iron from the malachite ore (acid concentration, 1.02 mol/L; temperature, 25
jC; particle size, 80%  650 Am; weight of ore, 25 g; solid/liquid, 1:10; time, 30 min).

leaching, the weight loss pattern was found similar to

malachite dissolution. Consequently, it was suggested
that the weight loss be related to the dissolution of
malachite. The recovery was 90% and the weight loss
was 40% for a solid to liquid ratio of 1:5.

3.5. Effect of temperature

As seen from Fig. 5, the copper recovery increased as the temperature was increased. The recovery after 120 min reached 94% and 98% for 25

Fig. 4. Effect of solid to liquid ratio (w/v) on the recovery of copper

from the malachite ore and on the weight loss during the leaching
(acid concentration, 1.02 mol/L; temperature, 25 jC; particle size,
80%  650 Am; weight of ore, 20 g; stirring speed, 250 rpm; time,
30 min).

Fig. 5. Effect of leaching time on the recovery of copper from the

malachite ore (acid concentration, 1.02 mol/L; temperature, 25 jC;
particle size, 100 150 Am; weight of ore, 25 g; solid/liquid ratio,
1:10; stirring speed, 350 rpm).

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163

3.6. Effect of particle size

The effect of particle size was studied using eight
crushed and five ground size fractions. For the copper
recovery calculations, the copper grade of each fraction was considered. These samples were all leached
using 1.02 mol/L sulphuric acid used at 25 jC. The
results are given in Figs. 6 and 7. From these figures,
it is clear that copper recovery is rapid at the beginning. If the particle size decreases, the dissolution is
more rapid. However, the particle size effect decreases
with increasing leaching times.

4. Discussion

jC and 80 jC, respectively. However, the malachite

dissolution hardly increased after a rapid dissolution
in 5 min.

Malachite can be easily dissolved by acidic reactions. The experimental results showed once more
that, as the amount of acid consumed is increased,
the dissolution of malachite increases (Fig. 8).
According to reaction (2), only about 90% of the
acid is used for malachite dissolution. The acid
consumption per mol malachite was found to be
2.22 2.37, the extra 10% is consumed in the dissolution of other minerals found in the ore, notably the
iron oxides.

Fig. 7. Effect of particle size of the ground ore for the dissolution of
malachite (acid concentration, 1.02 mol/L; temperature, 25 jC;
weight of ore, 25 g; solid/liquid ratio, 1:10; stirring speed, 350 rpm).

Fig. 8. The graph showing the direct relationship between the acid
consumption and the copper recovery.

Fig. 6. Effect of particle size of the crushed ore for the dissolution of
malachite (acid concentration, 1.02 mol/L; temperature, 25 jC;
weight of ore, 20 g; solid/liquid, 1:5; stirring speed, 250 rpm; time,
30 min).

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Accordingly, XRD analysis of the leaching residues showed malachite to be completely dissolved,
whereas goethite, magnetite, pyroxenes and quartz
were not dissolved in the acid leaching conditions
applied. It was also determined that the amount of
these gangue minerals in the residue increases as the
copper recovery or the amount of dissolved malachite increased.
Combining the chemical analysis and XRD analysis, it can be estimated that the ore consisted of
49.35% malachite, 22.56% goethite and magnetite,
27.36% quartz and pyroxene group, leaving only
0.73% unaccounted for by XRD analysis.
The kinetic evaluation of reactions occurring
during the acidic leaching of malachite indicated that
neither chemical nor diffusion models applied. These
models are unable to explain the dissolution of
malachite for the rapid initial reaction and the
complete leaching period studied. However, the
initial dissolution can be modelled using a logarithmic function: y = a ln(x) + b; where y is the copper
recovery, x is the leaching time, a and b are the
constant coefficients. A significant part of dissolution
has been achieved at the leaching times within 15
min and the values can be expressed by logarithmic

Fig. 10. The Arrhenius curve obtained for the dissolution of

malachite ore.

curves as presented in Fig. 9. It was also observed

that the values of a and b increase as the temperature
increases. The value of a increased from 3.539 at 25
jC to 3.735 at 80 jC and the value of b increases
from 81.683 to 86.141 over the same temperature
range.
It is possible to calculate the dissolution rate after
0.1 min of leaching at different temperatures by
using the model. From these rates, an Arrhenius
curve can be drawn (Fig. 10). It was determined that
the activation energy, Ea, was 1.3 kJ/mol. This value
is very low and indicates that the dissolution of
malachite is solution diffusion-controlled during the
initial dissolution. This is supported by the significant increase in dissolution due to stirring (Fig. 3).
After the initial dissolution, the availability of readily
accessible malachite had been greatly reduced and a
change in rate determining step is likely.

5. Conclusions

Fig. 9. Effect of time on the dissolution of malachite at 40 jC

leaching temperature (acid concentration, 1.02 mol/L; temperature,
25 jC; particle size, 100 150 Am; weight of ore, 20 g; stirring
speed, 350 rpm).

The following conclusions can be drawn from the

kinetic study of the malachite dissolution:
(i) Malachite was readily dissolved by sulphuric
acid giving high recoveries of copper, other

D. Bingol, M. Canbazoglu / Hydrometallurgy 72 (2004) 159165

minerals, such as iron minerals, were only

slightly affected from sulphuric acid medium.
(ii) The most important parameters affecting the
leaching were time, acid concentration, stirring
speed and the temperature of medium. Acid
concentrations of less than 1.02 mol/L were
insufficient for complete dissolution, for higher
concentrations there is a direct relationship
between the acid concentration and the dissolution of malachite. Leaching was found to
comprise two steps, an initial, very rapid
dissolution with f 85% copper recovery within f 15 min and a slower second step. After
210 min of leaching, the effect of particle size
on dissolution was found to be negligible. The
malachite dissolution increased slightly with
temperature, going from 94% to 98% as the
temperature increased from 25 to 80 jC.
(iii) The initial dissolution kinetics may be modelled
by a simple logarithmic function. From this
model, the activation energy was found to be
1.3 kJ/mol, clearly malachite dissolution is
controlled by solution diffusion.
(iv) Sulphuric acid consumption for 90% copper
recovery was computed to be about 450 kg per
ton ore.

165

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