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Investigation of Leaching Kinetics of Copper from Malachite Ore

in Ammonium Nitrate Solutions


AHMET EKMEKYAPAR, EVRIM AKTAS, ASIM KUNKUL,
and NIZAMETTIN DEMIRKIRAN
The production of metallic copper from low-grade copper ores is generally carried out by
hydrometallurgical methods. Leaching is the rst prerequisite of any hydrometallurgical process. Solutions containing ammonia may allow for selective leaching of the copper from the ore.
In this study, the leaching kinetics of malachite, which is an oxidized copper ore, in ammonium
nitrate solutions was examined. The eects of some experimental parameters on the leaching
process were investigated, and a kinetic model to represent the eects of these parameters on the
leaching rate was developed. It was determined that the leaching rate increased with increasing
solution concentration, temperature, and agitation speed, as well as decreasing particle size. It
was found that the leaching reaction followed the mixed kinetic controlled model, which
includes two dierent leaching processes including the surface chemical reaction (303 K to
323 K [30 C to 50 C]) and diusion through a porous product layer (323 K to 343 K [50 C to
70 C]). The activation energies of these sequential steps were determined to be 95.10 and
29.50 kJ/mol, respectively.
DOI: 10.1007/s11663-012-9670-2
The Minerals, Metals & Materials Society and ASM International 2012

I.

INTRODUCTION

IN the literature, oxide and sulde copper ores


mainly are known as azurite, malachite, tenorite,
chrysocolla, brochantite, enargite, chalcopyrite, chalcocite, covellite, and bornite.[1] The production of metallic
copper from these ores is carried out by pyrometallurgical and hydrometallurgical methods.[2] Pyrometallurgical methods are generally applied to the relatively
high-grade sulde copper ores. Increasingly, the lowgrade copper ores and secondary sources containing
copper are being used for the production of copper
because of depletion of high-grade copper ores at the
present time.[3] Pyrometallurgical methods are not
normally suitable for the processing of low-grade ores.
Instead, hydrometallurgical methods are usually preferred for the recovery of copper from these kinds of
ores.
Leaching is the term applied to the process of
recovering a metal from the metal source by a solvent
or lixiviant, and it is typically the rst step of any
hydrometallurgical process.[4] In the leaching process,
strong acids, such as HCl, HNO3, and H2SO4, are
commonly used as the leaching reagents.[5] Sulfuric acid
is the preferred lixiviant in the leaching of the oxidized
copper ores, such as azurite, malachite, tenorite, and
chrysocolla.[2,6] However, during the leaching of ores,
AHMET EKMEKYAPAR and ASIM KUNKUL, Professors, and
_
_ DEMIRKIRAN,
_
NIZAMETT
IN
Assistant Professor, are with the
Chemical Engineering Department, Faculty of Engineering, Inonu
University, Malatya 44280, Turkey. Contact e-mail: nizamettin.
_
demirkiran@inonu.edu.tr EVRIM
AKTAS, Chemical Engineer, is
with the Malatya Sugar Factory, Malatya 44080, Turkey.
Manuscript submitted September 22, 2011.
METALLURGICAL AND MATERIALS TRANSACTIONS B

other metals in ore matrix are also dissolved along with


the copper. These undesired impurities cause some
problems in further processing of the leaching solution,
such as the electrowinning of copper.[7] In addition, the
impurities in the ore can cause a high consumption of
acid. For these reasons, the use of solutions more basic
than sulfuric acid can be attractive in the leaching of
oxidized copper ores. For example, ammoniacal leaching systems have some advantages over acid leaching
systems. In the ammoniacal leaching system, the dissolution of ore can be carried out at mildly acidic or basic
conditions. Second, ammonia can be recovered by
evaporation. Furthermore, some metals, which pass
into the solution during the leaching process, precipitate
because of the higher pH of solutions containing
ammonia. Ammonia also forms stable complexes with
copper ions, which can lead to an increase in the
leaching rate from the ore. Thus, ammonia allows for
selective extraction of the copper from ore, leaving the
undesired components in the residue.[79] As a result, at
the end of the leaching process, a high purity solution
can be obtained for the electrolytic recovery of copper.
The leaching and kinetics of malachite, which is an
oxidized copper ore, in ammonia-containing solutions
has been investigated by various researchers. Oudenne
and Olson[10] studied the leaching kinetics of malachite
in ammonium carbonate solutions. They reported that
the leaching of malachite took place in two stages. At
the rst stage, the dissolution of malachite proceeded
rapidly. Then, the dissolution rate decreased because the
surface was coated from the formation of a needlestructured intermediate product, which is most likely
Cu(OH)2. Subsequently, malachite and the intermediate
product dissolved concurrently. The second stage of
leaching begun when essentially all the malachite was

dissolved and only the remaining intermediate phase


remained leached. It was determined that the activation
energies of these two stages were 64 and 75 kJ/mol,
respectively. Kunkul et al.[11] examined the dissolution
of malachite in ammonia solutions. They stated that the
leaching process was controlled by diusion through the
surface product layer. The activation energy of this
process was found to be 22 kJ/mol. A kinetic study was
performed by Yartas and Copur[12] on the dissolution
of malachite in ammonium chloride solutions. This
study also showed that the leaching rate was controlled
by diusion through the product layer. Ekmekyapar
et al.[7] investigated the dissolution kinetics of malachite
in ammonium chloride solutions. They determined that
the leaching rate was controlled by the mixed kinetic
model. A semiempirical mathematical model was also
suggested to represent the reaction kinetics. The activation energy for the malachite leaching reaction was
calculated to be 71 kJ/mol. A study was performed by
Arzutug et al.[2] with water saturated by ammonia gas
chosen as lixiviant. They determined that the leaching
rate of malachite in ammonia-saturated water increased
with decreasing particle size and solid-to-liquid ratio
and increasing reaction temperature, ammonia concentration, and agitation speed. The rate of dissolution t a
homogeneous pseudosecond-order kinetic model with
activation energy of 85 kJ/mol. The dissolution kinetics
of malachite in ammonia/ammonium carbonate solutions was examined by Bingol et al.[13] In this study, the
eects of leaching time, ammonium hydroxide, and
ammonium carbonate concentration, solution pH,
ammonia/ammonium ratio, agitation speed, solid-toliquid ratio, particle size, and reaction temperature on
the dissolution of malachite were investigated. They
found that the leaching process was controlled by the
interface transfer and diusion across the product layer.
Recently, Lui et al.[14] investigated the dissolution kinetics of low-grade complex copper ore, composed of
mainly malachite, chrysocolla, and bornite, in ammonia
ammonium chloride solutions. In this study, the eects
of various parameters on the dissolution of copper ore
were examined, and it was determined that the leaching
process was controlled by diusion through the surface
product layer around the shrinking unreacted core.
The use of ammoniacal systems in the leaching of ores
mostly seems to be feasible chemically. Ammonium
nitrate was chosen as lixiviant in the current study, and
the leaching and kinetics of malachite were investigated
in detail. The use of ammonium nitrate solutions has
some advantages over other ammoniacal systems. One
of the most important characteristics of leaching in
ammonium nitrate solutions is that the pH is essentially
constant during the leaching process. In addition,
ammonium nitrate provides ammonium ions, which
contributes the hydronium ions required for the dissolution of the ore. Ammonia produced by a reaction with
the ammonium ion forms stable complexes with Cu2+
ions, which leads to an increase in the dissolution rate of
the copper minerals. Because ammonium nitrate solutions have mildly acidic character (pH 5.1 to 5.5, in the
current study), ferric ions (Fe3+) passing into the
solution during the leaching process precipitate in the

form of Fe(OH)3. Thus, a high-purity solution can be


obtained.
The aim of this study is to investigate and discuss the
leaching kinetics and dissolution parameters of malachite in ammonium nitrate solutions.

II.

MATERIALS AND METHODS

An oxidized copper ore sample (malachite) used in


this study was provided from the mine in Ovack,
Tunceli, Turkey. The ore sample was crushed, ground,
and then sieved using standard test sieves to obtain
desired particle size fractions. The mineralogical analysis
of the ore sample was performed using a Rigaku RadBDMAX II model X-ray diractometer (Rigaku Corporation, The Woodlands, TX). The result of the X-ray
analysis given in Figure 1 indicates that the sample
contains mainly malachite (CuCO3Cu(OH)2), quartz
(SiO2), and smithsonite (ZnCO3). Malachite mineral in
the ore matrix has a monoclinic crystal structure. The
chemical analysis result of the sample is given in Table I.
The leaching experiments were carried out in a 750mL cylindrical glass reactor equipped with a mechanical
agitator, a reaction temperature control unit, and a
condenser to avoid loss of solution from evaporation.
The experimental procedure was initiated by adding
500 mL of an ammonium nitrate solution into the glass
reactor and bringing it to the desired reaction temperature. A given amount of solid sample was then added
to the solution. The dissolution process was carried out
for various reaction times. Aliquots of 5 mL were
withdrawn at regular intervals during the reaction and
were immediately ltered. The amount of dissolved
copper in the solution was determined complexometrically using ethylenediaminetetraacetic acid solution as

Fig. 1X-ray diraction pattern for oxidized copper (malachite) ore


used in the study.
METALLURGICAL AND MATERIALS TRANSACTIONS B

Table I.

Chemical Analysis of Malachite Ore Used in the Study

Component

SiO2

ZnO

CuO

Fe2O3

Al2O3

Ignition Loss

Other Oxides
(Na, Ca, K, Mg, Oxides)

Value, pct

50.41

15.23

10.55

8.43

1.81

12.40

1.17

Table II. Leaching Parameters and the Ranges Used in the


Leaching Experiments
Parameter

Value

Concentration (mol/L)
Temperature [K (C)]
Agitation speed (rpm)
Average particle size (lm)

2, 3, 4*, 5
303 (30), 313 (40)*, 323 (50),
333 (60), 343 (70)
200, 300, 400*, 500
136, 120, 93, 71.5, 62.4*

*These parameters were kept constant.

titrant and murexide as indicator. The conversion


fraction of malachite was calculated as follows:
x = mass of copper passing to the solution/mass of
copper in the ore sample.
The leaching rate of malachite was determined as a
function of time by changing the ammonium nitrate
concentration, particle size, agitation speed, and reaction temperature. In the experiments, while the eect of
one parameter was investigated, the values of other
parameters shown with an asterisk in Table II were kept
constant. The leaching data obtained were plotted as a
function of conversion fraction x vs reaction time t.

III.

RESULTS AND DISCUSSION

A. Leaching Reactions
Ammonium nitrate is the salt of a strong acid (HNO3)
and a weak base (NH3), and it has a weakly acidic
character. Ammonium nitrate ionizes in aqueous
medium according to the following reaction:

NH4 NO3 ! NH
4 NO3

1

The ammonium ion is hydrolyzed

NH
4 H2 O  NH3 H3 O

2

Ammonia and hydronium ion formed by the hydrolysis


reaction play an important role in the leaching process.
The ammonium ion provides the protons (hydronium
ion) required for the dissolution of basic malachite ore,
whereas the ammonia produced forms stable complexes
with copper (II) ions passing dissolved from the ore. The
formation of these complexes leads an increase in the
leaching rate of malachite ore.
The copper in the malachite ore is in the form of
CuCO3Cu(OH)2. When malachite ore is added into
ammonium nitrate solution, the reactions occurring
during the leaching process are expected to be

METALLURGICAL AND MATERIALS TRANSACTIONS B

4

Copper ions passing into the solution form copper


amine complexes with ammonia, and thus, no precipitation of copper occurs from the solution. The formation reactions of the copper amine complexes are
written as follows:
Cu2 2NH3  CuNH3 2
2

5

2
CuNH3 2
2 2NH3  CuNH3 4

6

formed during the


It is reported that the Cu(NH3)2+
2
leaching reaction is an intermediate species, and it
[2,7]
converts to the stable complex of Cu(NH3)2+
4 .
Consequently, the overall leaching reaction can be
written as follows:
CuCO3 CuOH2 4NH4 NO3
! 2Cu2 4NH3 4NO
3 CO2 3H2 O

7

B. Effects of Ammonium Nitrate Concentration


To investigate the eect of ammonium nitrate concentration on the leaching rate, the experiments were
carried out using from 2 to 5 mol/L of ammonium
nitrate. In these experiments, the reaction temperature,
solid-to-liquid ratio, particle size, and agitation speed
were kept at 313 K (40 C), 2 g solid/0.5 L solution,
62.4 lm, and 400 rpm, respectively. The results obtained
from these experiments were plotted in Figure 2. This
gure shows that the leaching rate increases with an
increase in lixiviant concentration. After 150 minutes of
leaching, the copper extraction from the ore was 62.9 pct,
70.6 pct, 82.3 pct, and 87.8 pct at 2, 3, 4, and 5 mol/L of
concentration, respectively. It is clear from these results
that the extents of copper extraction from the ore
increased with increasing lixiviant concentration.
C. Effect of Particle Size
The eect of particle size on the leaching of copper
from the malachite ore was examined by using fractions
of the ore with average particle size of 136, 120, 93, 71.5,
and 62.4 lm. In these experiments, the values of other
parameters were kept constant at 4 mol/L, 313 K
(40 C), 2 g solid/0.5 L solution, and 400 rpm. Figure 3
shows the eect of particle size on the leaching rate. It
can be observed from this gure that the dissolution rate
increases with decreasing particle size.
D. Effect of Stirring Speed

CuCO3 CuOH2 2H3 O ! Cu2 CO2


3H2 O CuOH2

CuOH2 2H3 O ! Cu2 4H2 O

3

The eect of the agitation speed on the leaching of the


malachite ore was studied by testing agitation speeds of

200, 300, 400, and 500 rpm while the values of the
solution concentration, reaction temperature, solid-toliquid ratio, and particle size were kept constant at
4 mol/L, 313 K (40 C), 2 g solid/0.5 L solution, and
62.4 lm, respectively. The results are given in Figure 4.
After 150 minutes of leaching, the extent of leaching of
copper from the ore increased from 72 pct to 89.8 pct
when the agitation speed increased from 200 to 500 rpm.
The experimental ndings indicate that the agitation
speed is a major factor in the leaching of the malachite
ore.

E. Effect of Reaction Temperature


To determine the eect of the reaction temperature on
copper extraction from the malachite ore, the experiments were carried out at ve dierent temperatures in
the range of 303 K to 343 K (30 C to 70 C). While
conducting these experiments, the values of other
experimental parameters were kept constant at 4 mol/L,
2 g solid/0.5 L solution, 62.4 lm, and 400 rpm. From
the results plotted in Figure 5, the leaching rate
increases considerably with higher reaction temperatures. The reaction temperature has a signicant eect
on the extent of copper extraction from malachite ore.
At a temperature of 303 K (30 C), 55 pct of copper was
extracted after 150 minutes of leaching, whereas at a
temperature of 343 K (70 C), 98 pct of copper was
extracted only after 75 minutes of leaching.
F. Kinetic Study

Fig. 2Eect of ammonium nitrate concentration on leaching of


malachite ore.

Fig. 3Eect of particle size on leaching of malachite ore.

Increasing attention is being paid to the study of the


chemical kinetics of nonhomogeneous systems. In the
classic homogeneous systems, the usual rate laws of
rst- and second-order kinetics are often sucient to
explain and analyze the experimental data.[15] Leaching
is a central unit operation in the hydrometallurgical
treatment of ores, and the reactions occurring during the
leaching process are typically heterogeneous. Thus,
leaching reactions do not often obey simple rst- and
second-order kinetics. A kinetic analysis of these kinds
of reactions is generally performed by noncatalytic
heterogeneous reaction models. A kinetic analysis of
leaching reactions is required for the eective design of
leaching reactors for use in a hydrometallurgical
plant.[15,16]
The leaching reaction of mineral particles by a reagent
(a soliduid reaction) can be represented by the
following reaction:

Fig. 4Eect of agitation speed on leaching of malachite ore.


METALLURGICAL AND MATERIALS TRANSACTIONS B

If the reaction rate is controlled by the diusion


through the ash or product layer, then the integrated
rate expression is
1  31  x2=3 21  x kd t

10

If the leaching rate is controlled by the surface


chemical reaction, then the integrated rate equation is
1  1  x1=3 kr t

Fig. 5Eect of reaction temperature on leaching of malachite ore.

Afluid bBsolid ! fluid and=or solid products

8

where A, B, and b represent the uid reactant, the solid


undergoing leaching, and stoichiometric coecient,
respectively. The kinetic of leaching reactions is often
described by the shrinking core model. According to the
shrinking core model, it is thought that the reaction
between solid and uid reactants takes place on the outer
surface of solid. The solid reactant is initially surrounded
by a uid lm through which mass transfer occurs
between the solid and the bulk uid. As the reaction
proceeds, the unreacted core of the solid shrinks toward
the center of the solid, and a porous product layer forms
around the unreacted core. However, it is assumed that
the initial outside radius of the solid does not change
while the leaching reaction continues.[5,1719]
The leaching rate of solid is governed by physical and
chemical factors. The governing factors are the rate of
transport of uid reactant to and products from the
particle surface (i.e., diusion through the uid lm), the
rate of diusion of uid reactant and products through
the porous product layer that forms on the unreacted
core of solid (i.e., diusion through the product layer),
and the rate of the reaction at the surface of unreacted
core (i.e., surface chemical reaction). Each of these
phenomena aects the rate of the overall leaching
reaction. One or more of these factors might control
the rate of reaction.[16] For each step mentioned, the
integrated rate equations derived from the shrinking
core model are given in the literature.[17,18,20] These rate
equations can be written as follows:
If the leaching rate is controlled by the diusion
through the liquid lm, then the integrated rate equation
is
x kl t
METALLURGICAL AND MATERIALS TRANSACTIONS B

9

11

where x is the conversion fraction of solid particle, kl is


the apparent rate constant for diusion through the
uid lm, kd is the apparent rate constant for diusion
through the product layer, kr is the apparent rate
constant for the surface chemical reaction, and t is the
reaction time.
To determine the kinetic parameters and rate-controlling step of the leaching of malachite in ammonium
nitrate solutions, the data obtained in the leaching
experiments were analyzed based on the shrinking core
model using the rate expression given in Eqs. [9] through
[11]. By applying the rate expression in Eqs. [9] through
[11] to the experimental data obtained, the apparent rate
constants were calculated. To obtain the apparent rate
constants of each step, the left side of Eqs. [9] through
[11] was plotted vs the reaction time for each parameter,
and the slopes of the straight lines passing through the
origin were equalling the rate constants. For each
experimental parameter, the apparent rate constant
values obtained from the plots and the correlation
coecients are provided in Table III. As can be observed
from the data in Table III, the low regression coecients
were obtained for the lm diusion and the chemical
reaction models, indicating that neither of these processes represent the rate-controlling step. From Table III,
the largest regression coecients were obtained for the
diusion through the product layer model, indicating
that the diusion through the product layer acts as the
rate-controlling step in this leaching system. This observation is supported by the experimental observations and
ndings as shown in Figure 6, which is plot of 1 3(1
x)2/3+2(1 x) vs time for dierent particle sizes.
However, if the leaching reaction is controlled by
diusion through the product layer, then the leaching
rate should not be sensitive to the reaction temperature.
However, as shown in Figure 5, the leaching reaction of
malachite was quite sensitive to temperature. Therefore,
to dene the rate-determining step of this process, the
mixed kinetic models were tested using the experimental
data. These kinds of kinetic models have been described
in the literature.[7,13,17,21,22] Among the mixed kinetic
models tested, it was found that the following model
could be more suitable to represent the kinetics of the
dissolution of malachite in ammonium nitrate solutions.
1  21  x1=3 1  x2=3 km t

12

where km is the apparent rate constant for the mixed


kinetic model.
To test the validity of the model in Eq. [12], the left
side of Eq. [12] vs time was plotted for the solution

Table III.

The Apparent Rate Constants, kl, kr, and kd for Kinetic Models and Correlation Coecient Values
Diffusion Through the
Liquid Film
X

Parameter

kl (min1)

Concentration (mol/L)
2
3
4
5
Temperature [K (C)]
303 (30)
313 (40)
323 (50)
333 (60)
343 (70)
Stirring speed (rpm)
200
300
400
500
Particle size (lm)
136
120
93.0
71.5
62.4

Surface Chemical Reaction


1 (1 x)1/3

Diffusion Through the


Product Layer
1 3(1 x)2/3 + 2(1 x)

R2

kr (min1)

R2

kd (min1)

R2

0.0050
0.0057
0.0067
0.0074

0.627
0.576
0.572
0.422

0.0021
0.0025
0.0032
0.0038

0.788
0.786
0.834
0.790

0.0013
0.0017
0.0026
0.0034

0.996
0.996
0.998
0.990

0.0043
0.0067
0.0093
0.0120
0.0167

0.722
0.572
0.390
0.332
0.285

0.0017
0.0032
0.0056
0.0073
0.0103

0.840
0.834
0.873
0.851
0.827

0.0009
0.0026
0.0057
0.0076
0.0107

0.995
0.998
0.992
0.986
0.980

0.0058
0.0062
0.0067
0.0073

0.630
0.575
0.572
0.473

0.0026
0.0029
0.0032
0.0038

0.820
0.800
0.834
0.817

0.0017
0.0021
0.0026
0.0038

0.997
0.991
0.998
0.993

0.0049
0.0053
0.0057
0.0062
0.0067

0.752
0.694
0.057
0.652
0.572

0.0021
0.0023
0.0025
0.0029
0.0032

0.874
0.847
0.860
0.850
0.834

0.0012
0.0014
0.0017
0.0021
0.0026

0.996
0.997
0.997
0.998
0.998

Fig. 6Plot of 1 3(1 x)2/3+2(1 x) vs time for dierent particle


sizes.

concentration, agitation speed, particle size, and temperature. The graphs obtained are given in Figures 7
through 10. The apparent rate constants calculated from
the slopes of the straight lines in Figures 7 through 10 and
their correlation coecients are given in Table IV. From
the results shown in Figures 7 through 10 and in
Table IV demonstrate that the kinetic model in Eq. [12]
is appropriate to explain this leaching process.

Fig. 7Plot of 1 2(1 x)1/3 + (1 x)2/3 vs t for dierent lixiviant


concentrations.

To determine the eects of the reaction parameters on


the reaction rate constant, the following mathematical
model can be suggested:
km ko :Cc :PSp :SSr : expEa =RT

13

where C, PS, SS, Ea, R, and T represent the concentration, particle size, stirring speed, activation energy,
METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 8Plot of 1 2(1 x)1/3 + (1 x)2/3 vs t for dierent particle


sizes.

The constants c, p, and r were estimated from the


apparent rate constant values given in Table IV. The
plots of ln(km) vs ln(C), ln(km) vs ln(PS), and ln(km) vs
ln(SS) were constructed using the values given in
Table IV for each parameter. The slopes of the straight
lines in the graphs obtained assign the reaction order for
each parameter. The values of the constants c, p, and r
were determined to be 0.80, 1.04, and 1.02, respectively.
The activation energy of this leaching process was
estimated from the Arrhenius equation. The Arrhenius
plot of the reaction is shown in Figure 11. As can be
observed from this gure, two straight lines were
obtained. This situation indicates that the leaching
reaction is controlled by two dierent leaching
processes.
A shift in the activation energy at 323 K (50 C) is
probably a result of the change in the reaction mechanism. The lines in Figure 11 show the variations
between 303 K to 323 K (30 C to 50 C) the rst zone
(surface reaction) and 323 K to 343 K (50 C to 70 C)
the second zone (product layer diusion). At temperatures below 323 K (50 C) (i.e., the rst zone), the
activation energy and the preexponential factor were
calculated to be 95.10 kJ/mol and 7.79 9 109 s1,
respectively. At temperatures above 323 K (50 C)
(i.e., the second zone), these values were determined to
be 29.50 kJ/mol and 5.3 s1, respectively.
In the literature, it is stated that the diusion
controlled heterogeneous reactions are slightly dependent on temperature, while chemically controlled processes are strongly dependent on temperature. The
activation energy of a diusion controlled process is
usually below 40 kJ/mol, while for a chemically controlled reaction this value is usually greater than 40 kJ/
mol.[23,24] Therefore, the value of the activation energy

Fig. 9Plot of 1 2(1 x)1/3 + (1 x)2/3 vs t for dierent agitation


speeds.

Fig. 10Plot of 1 2(1 x)1/3 + (1 x)2/3 vs t for dierent temperatures.

universal gas constant, and temperature, respectively.


The constants c, p, and r are the reaction order for
relating parameters, and ko is the frequency or preexponential factor.
Combining Eqs. [12] and [13], the following equation
is obtained:
1  21  x1=3 1  x2=3
ko :Cc :PSp :SSr : expEa =RT:t

METALLURGICAL AND MATERIALS TRANSACTIONS B

14

of a leaching reaction may be used to predict the rate


controlling step of the process. According to the
activation energies values determined in this study, the
rate of process is controlled by the surface chemical
reaction in the rst zone (i.e., less than 323 K [50 C])
and by the diusion through the product layer in the
second zone (i.e., greater than 323 K [50 C]). As a

Table IV. The Apparent Rate Constant, km, for Mixed


Kinetic Model and Correlation Coecient Values
Mixed Kinetic Model
1 2(1 x)1/3 + (1 x)2/3
Parameter
Concentration (mol/L)
2
3
4
5
Temperature (K (C))
303 (30)
313 (40)
323 (50)
333 (60)
343 (70)
Stirring speed, rpm
200
300
400
500
Particle size, lm
136
120
93.0
71.5
62.4

km (min1)

R2

0.0005
0.0008
0.0011
0.0016

0.998
0.998
0.997
0.999

0.0003
0.0011
0.0031
0.0041
0.0059

0.992
0.997
0.994
0.996
0.998

0.0006
0.0009
0.0011
0.0015

0.997
0.997
0.997
0.999

0.0005
0.0006
0.0007
0.0009
0.0011

0.992
0.995
0.997
0.998
0.997

Fig. 11Arrhenius plot for leaching process.

result, the kinetic expressions including the reaction


parameters used in this leaching process can be written
for the two regions as follows:
1  21  x1=3 1  x2=3
7:79  109 C0:80 PS1:04 SS1:02 exp11438=T:t
15
(for 303 K to 323 K [30 C to 50 C])
1  21  x1=3 1  x2=3
5:3C0:80 PS1:04 SS1:02 exp3558=T:t

16

(for 323 K to 343 K (50 C to 70 C))


G. Analysis of Leach Residue
To determine the mineralogy of dissolved malachite
ore, the X-ray diraction (XRD) analysis of the solid
residue obtained after leaching process was performed.
The result of XRD analysis relating to leach residue is
given in Figure 12. It can be observed from Figure 12
that the peaks of CuCO3Cu(OH)2 (malachite) and
ZnCO3 (smithsonite) disappear while quartz and Fe
remain in the leach residue. This result shows that
malachite ore can be leached by using ammonium
nitrate solutions. The resulting leach solution contains
copper and zinc amine complexes.
IV.

CONCLUSIONS

In this study, the leaching kinetics of malachite ore


was studied using ammonium nitrate solutions as the
lixiviant. The eects of several experimental parameters

Fig. 12X-ray diraction pattern of the solid residue resulting from


leaching of malachite ore.
METALLURGICAL AND MATERIALS TRANSACTIONS B

on the extraction of copper from the ore were examined,


and kinetic evaluations were made. It was determined
that the leaching rate of copper increased with increasing concentration, temperature and stirring speed, and
decreasing particle size. It was found that the leaching
reaction investigated followed the mixed kinetic control
model, which contains two sequential mechanisms. The
leaching rate is controlled by the surface chemical
reaction at temperatures between 303 K and 323 K
(30 C and 50 C) (Ea = 95.10 kJ/mol), while it is
controlled by diusion through the product layer at
temperatures between 323 K and 343 K (50 C and
70 C) (Ea = 29.50 kJ/mol). A mathematical model
containing experimental parameters to represent the
reaction kinetics in this leaching system was constructed.

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