J. Cent. South Univ.

(2012) 19: 903−910

DOI: 10.1007/s11771-012-1091-5

Dissolution kinetics of malachite in ammonia/ammonium sulphate solution

LIU Zhi-xiong(刘志雄)1, 2, YIN Zhou-lan(尹周澜)1, HU Hui-ping(胡慧萍)1, CHEN Qi-yuan(陈启元)1

1. School of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China;
2. College of Chemistry and Chemical Engineering, Jishou University, Jishou 416000, China
© Central South University Press and Springer-Verlag Berlin Heidelberg 2012

Abstract: The dissolution kinetics of malachite was investigated in ammonia/ammonium sulphate solution. The effects of ammonia
and ammonium sulphate concentration, pH, leaching time, reaction temperature, and particle size were determined. The results show
that the optimum leaching conditions for malachite ore with a copper extraction more than 96.8% are ammonia/ammonium
concentration 3.0 mol/L NH4OH + 1.5 mol/L (NH4)2SO4, liquid-to-solid ratio 25:1 mL/g, leaching time 120 min, stirring speed 500
r/min, reaction temperature 25 °C and particle size finer than 0.045 mm. The dissolution process of malachite with an activation
energy of 26.75 kJ/mol is controlled by the interface transfer and diffusion across the product layer. A semi-empirical rate equation is
obtained to describe the leaching process and the reaction orders with respect to concentration of ammonia and ammonium sulphate
are 2.983 0 and 0.941 1, respectively.

Key words: copper; malachite; kinetics; ammonia; ammonium sulphate

occurs as a secondary copper mineral in the upper

1 Introduction oxidized zone of copper deposits, and it is soluble in acid
medium. The leaching kinetics of malachite in sulfuric
Copper generally is found in nature in the form of acid [8−9] and the extraction of copper from raffinate via
oxidized and sulfide minerals, such as azurite solvent extraction (SX) have been studied intensively
[Cu3(OH)2(CO3)2], malachite [Cu2(OH)2CO3], [10−11].
chrysocolla (CuSiO32H2O), chalcopyrite (CuFeS2) However, acid leaching of oxidized copper ores has
covelline (CuS) and bornite (Cu5FeS4 ). In the past years, some disadvantages. Not only azurite, malachite and
copper was mostly produced from sulfide ores by copper silicates will consume acid, but also other gangue
pyrometallurgical operations because sulfide ores are minerals, such as limestone and dolomite, usually
easily separated from gangue and concentrated by consume acid [12−13]. The preponderance of carbonates
conventional flotation techniques. Recently, the depletion in copper ores often causes excessive increase in the acid
of high-grade copper sulfide ores has led to the focusing consumption. Moreover, many other metals, such as Fe,
on the extraction of copper from oxidized copper ores in and Al, can be dissolved with sulfuric acid, which brings
various carbonate and silicate minerals [1−6]. about the difficulty of purification. Therefore, a
Unlike copper sulfides treated by pyrometallurgical cost-effective leaching route needs to be developed and
operations, the processing of oxidized copper ore needs more selective reagents are necessary for the processing
to follow different approaches. The oxidized copper ores of oxidized copper ores. Alkaline leaching, which is
are soluble either in acidic or alkaline medium at room more selective, less corrosive and has lower reagent
temperature. Hydrometallurgical methods of processing consumption for calcareous or carbonated gangue, has
ores or their concentrates have an increasing importance attracted a lot of interests of researchers.
in the extraction of oxidized copper ore. Sodium hydroxide, lime and ammonia are the most
Hydrometallurgical processes including leaching, solvent commonly used alkaline reagents. A large number of
extraction and electrowinning (L-SX-EW) were applied leaching systems in which complex ions are formed
[7]. Sulfuric acid is the most usual lixiviant for oxidized between the metal cation and complexing species in
copper ore, and owing to the different nature of ores, acid solutions are widely utilized. Ammonium hydroxidized is
consumption ranges from 0.4 to 0.7 t H2SO4 for 1 t copper extensively used in nickel, cobalt, and copper industries
recovered. Among oxidized copper minerals, malachite due to the formation of metal-ammonia complexes which

Foundation item: Project(2007CB613601) supported by the National Basic Research Program of China; Project(10C1095) supported by the Foundation of
Hunan Educational Committee, China
Received date: 2011−05−20; Accepted date: 2011−09−19
Corresponding author: YIN Zhou-lan, Professor, PhD; Tel: +86−731−88877364; E-mail: [email protected]
904 J. Cent. South Univ. (2012) 19: 903−910
are highly soluble in ammonia and ammonium salt ammonia/ammonium sulphate solution is investigated to
solutions. Ammonium hydroxidized or ammonia/ provide basal data for industry.
ammonium carbonate/chlorite leaching system is
commonly applied in the leaching of malachite [14−18]. 2 Experimental
ARZUTUG et al [14] studied the dissolution of
malachite in NH3-saturated water solution and examined 2.1 Materials
the leaching kinetics by applying statistical method to the The oxidized copper ore, which was a specimen
experimental data. They claimed that the leaching rate mineral, was from Tangdan, Yunnan Province, China.
was fitted to a pseudo-second-order kinetic model with The chemical composition of the sample ore is listed in
an activation energy of 85.16 kJ/mol. Table 1. The element contents of copper, iron,
BINGŐL et al [17] investigated the dissolution of magnesium, chromium, calcium and manganese were
malachite in ammonia/ammonium carbonate medium analyzed using an atomic absorption spectrophotometer
and found that the leaching process was controlled by the (AAS). Zn content was determined by inductively
interface transfer and diffusion across the product layer coupled plasma atomic emission spectroscopy (ICP-
and that the activation energy was 15 kJ/mol. YARTAŞI AES, Thermo Fisher Scientific, IRIS Intrepid II XSP).
and ÇOPUR [18] studied the dissolution kinetics of Sulfur was determined by LECO-444SC analyzer. Quartz
malachite in ammonium chloride solution and a content was analyzed by classical digestion with HF
mathematical model was derived for the dissolution method.
process which is controlled by diffusion through the
product film. Table 1 Main chemical compositions of oxidized copper ore
KŰNKŰL et al [19] studied the leaching kinetics of (mass fraction, %)
malachite in ammonia solution and deduced a Cu Ca Mg Al Fe
mathematical model for the leaching process with the
29.9 16.98 5.51 1.12 1.79
activation energy of 22.338 kJ/mol. They declared that
the leaching process was controlled by diffusion through Mn Zn Cr Si S
the ash film. A kinetic study performed by Oudenne and 0.18 0.198 0.08 7.58 0.08
Olson was reported that the leaching of malachite in
ammonium carbonate solution took place in two stages
Mineralogical analysis was performed by X-ray
[15]. The rate equations were defined as 1−(1−x)1/3=k1t
diffractometer using a Philips RigakuTM DMAX 2250VB
for stage I and 1−(1−x)1/2=k2t for stage II (where x is the model. As shown in Fig. 1, it was indicated that the
reaction fraction of the solid, k1 and k2 are rate constants,
major mineral phases in the sample were malachite,
and t is the leaching time). The activation energies were dolomite and quartz.
64 kJ/mol for stage I and 75 kJ/mol for stage II.
EKMEKYAPAR and OYA [20] suggested that the
dissolution rate of malachite in ammonium chloride
solution was controlled by mixture kinetics and that the
activation energy for the dissolution reaction was
calculated as 71 kJ/mol. The semi-empirical model
proposed to represent the reaction kinetics was
1−2(1−x)1/3+(1−x)2/3=kt.
Generally, these leaching kinetics investigations of
malachite have been carried out in acid, ammonia,
ammonia/ammonium carbonate and ammonia/
ammonium chloride media, but the leaching kinetic
characteristics of malachite in ammonia/ammonium
sulphate solutions have been rarely reported.
Tangdan oxidized copper ore, which contains Fig. 1 X-ray diffraction pattern of copper ore
high-grade calcium-magnesium carbonate gangues and
has poor floatable characteristics, is one of the largest The copper ore was crushed and ground by using
copper mine in China with a reserve of about 115×104 t. crusher, roller and mill, and sieved to gain the desired
Its average content of copper is 0.75% (mass fraction) particle size fractions of 0−0.045, 0.045−0.075, 0.075−
and the phase composition of copper is quite complex. 0.150 and 0.150−0.212 mm for the leaching experiments.
The specimen mineral of malachite was from Tangdan. The experiments regarding the effects of ammonia/
The leaching of the malachite ore in ammonium sulphate concentration, liquid-to-solid ratio,
J. Cent. South Univ. (2012) 19: 903−910 905
temperature and stirring speed were performed with the Cu 2 (OH)2 CO 3  6NH 4 OH  2(NH 4 ) 2 SO 4 →
ore sample of 0.100−0.150 mm. The experiments, in
2Cu(NH 3 ) 24  2SO 24  2NH 4  CO 32  8H 2 O (3)
which the effects of particle size were studied, were
carried out using ores with different sizes. pH
measurements were carried out with LEICI PHS-3C. 3.2 Effect of operation parameters on leaching of
Leaching solutions were prepared using reagent grade copper
chemicals (Ammonia, 25.7% NH3(aq); Ammonium 3.2.1 Effect of agitation speed
sulphate, 99.5%) and distilled water. The effect of agitation speed on the copper leaching
was carried out in the range from 100 to 500 r/min. An
2.2 Experimental procedure adequate suspension of the solid was observed at
A 500 mL round-bottomed split flask was used as a 300 r/min and the copper dissolution was independent of
leaching reactor with four necked tops for taking samples the agitation above this speed. As a result, agitation
from leaching solution. Mechanical stirrer, a mercury speed was maintained at 500 r/min subsequently to
thermometer and a cooler were used to avoid evaporation eliminate the effect of agitation as a variable on the
loss of solution and ammonia. The desired temperature leaching rate. It is only indicated that hydrodynamic
of the flask within the error of ±0.5 °C was adjusted by a boundary layer around the particle has reached a limited
thermo-statically controlled electric heating mantle. All value with the high stirring speed. Thus, diffusion across
experiments were controlled at temperatures between 15 this minimum thickness boundary layer could still be the
and 55 °C. Agitation was provided by a mechanical slow step. Therefore, additional experimental evidence
stirrer. The 200 mL solution containing specific such as the value of the activation energy and the
concentration of NH4OH/(NH4)2SO4 was added into the application of kinetics model are needed to determine the
leaching reactor. After the desired stirring speed and rate controlling step.
reaction temperature were attained, solid sample was 3.2.2 Effect of leaching time
added to the solution in reactor. At selected time intervals, The effect of leaching time on the dissolution of
2 mL of leaching solution sample was withdrawn from malachite was investigated. The results are shown in
the reactor and filtered for analysis. The sample solution Fig. 2. It is obvious that the extraction rate of copper
was analyzed for copper by an atomic absorbance
increases with increasing the leaching time. At the
spectrophotometer (AAS). At the same time, 2 mL fresh
beginning of leaching, the dissolution rate of malachite is
lixiviant was added into the reactor immediately to keep
very high. After 5 min, the copper extraction rate reaches
the volume of the solution constant. Filtration was made
53.0%. After 25 min, the copper extraction rate increases
after each leaching experiment. The residue was weighed
slowly. This can be explained by the reason that the
after being dried for 10 h at 110 °C.
malachite is mainly dissolved and the content of
malachite in the residue of leaching becomes lower. The
3 Results and discussion
copper extraction rate increases to 87.6% at the end of
3.1 Dissolution principles 180 min.
NH3 is a weak base and can form complexes with
Cu2+ in aqueous solution. Within a specified range of pH,
all of the complexes with Cu2+ in the solution are
water-soluble, and they belong mainly to Cu(NH 3 ) 24
complex in the ammonia/ammonium salt aqueous
solution whose pH value is between 9 and 12.
Malachite (Cu(OH)2CuCO3) dissolves in NH4OH/
(NH4)2SO4 solutions by forming a stable Cu(NH 3 ) 24
complex. The ammonia leaching reactions for malachite
take place as follows:

Cu(OH)2  2NH 4 OH  (NH 4 ) 2 SO 4 →

Cu(NH3 ) 4 SO 4  4H 2 O (1)

CuCO 3  4NH 4 OH  (NH 4 ) 2 SO 4 → Fig. 2 Effect of leaching time on copper extraction of malachite
Cu(NH3 ) 24  SO 24  4H 2 O  2NH 4  CO 32 (2) (Ammoniacal concentration 3.0 mol/L NH4OH + 1.5 mol/L
(NH4)2SO4; temperature 25 °C; particle size 0.100−0.150 mm;
The overall reaction for leaching can be written as liquid-to-solid ratio 20 mL/g; stirring speed 500 r/min)
906 J. Cent. South Univ. (2012) 19: 903−910
3.2.3 Effect of ammonia/ammonium concentration
The effects of ammonia concentration and pH of the
leaching solution were investigated in ammonia solution.
The results for the copper extraction and pH of the
leaching solution are shown in Fig. 3. It is shown that the
copper extraction rate increases with the increase of
ammonia concentration. The extraction rate of copper
increases greatly in the range of 0−5 mol/L NH4OH, and
then it increases slowly. pH of the leaching solution
increases with the increase of ammonia concentration.
The copper extraction rate of malachite can reach 73.4%
at 13.4 mol/L NH4OH, while it is only 7.5% at 1.0 mol/L
NH4OH.

Fig. 3 Effect of NH4OH concentration on copper extraction of Fig. 4 Effect of ammonia and ammonium sulphate
malachite and change of pH during leaching in ammonia concentration on copper extraction in ammonia/ammonium
solution (Temperature 25 oC; particle size 0.100−0.150 mm; solution (Temperature 25 oC; particle size 0.100−0.150 mm;
liquid-to-solid ratio 20 mL/g; stirring speed 500 r/min; time liquid-to-solid ratio 20/1 mL/g; stirring speed 500 r/min):
180 min) (a) Ammonia; (b) Ammonium sulphate

The effect of various ammonia/ammonium sulphate 3.0 mol/L ammonia + 1.5 mol/L ammonium sulphate
concentration for the leaching of malachite was solution was determined as lixiviant for the following
investigated in ammonia/ammonium sulphate solution. experiments.
These results of copper extraction are given in Fig. 4. 3.2.4 Effect of particle size of samples
These results proclaim that the copper extraction rate The effect of the particle size of samples on the
increases with leaching time for different ammonia and leaching of malachite was studied. The results are given
ammonium concentrations, respectively. The copper in Fig. 5. It is obvious that the extraction rate of copper
extraction rate increases with increasing ammonia increases as the particle size decreases. It can be taken
concentration (Fig. 4(a)) at ammonium sulphate for granted that the increase in the surface area causes
concentration of 1.5 mol/L. With the increase of better exposure of the malachite ore to solution with the
ammonia concentration, more reaction molecules attack decrease of the particle size.
the solid. The copper extraction rate increases with the 3.2.5 Effect of liquid-to-solid ratio
concentration of ammonium sulphate (Fig. 4(b)) at The effect of liquid-to-solid ratio from 5 to 30 mL/g
ammonia concentration of 3.0 mol/L. At the same on the leaching of malachite was investigated at 25 °C.
ammonia concentration, the copper extraction rate of The results are given in Fig. 6. The result indicates that
copper in ammonia/ammonium solution is higher than the increase of liquid-to-solid ratio can enhance the
that of copper in ammonia solution. This can be dissolution of copper. The larger the liquid-to-solid ratio,
explained by the fact that ammonia/ammonium solution the faster the leaching rate. This can be explained by the
is a buffer solution and provides constant pH at a certain fact that the amount of fluid reactant per unit surface of
value for better forming copper-ammonia complexes. the solid increases with the increase of liquid-to-solid
Considering ammonia volatility and low-cost production, ratio. However, there is no obvious change in copper
J. Cent. South Univ. (2012) 19: 903−910 907

Fig. 5 Effect of particle size on copper extraction of malachite Fig. 7 Effect of temperature on copper extraction of malachite
(Ammoniacal concentration 3.0 mol/L NH4OH + 1.5 mol/L (Ammoniacal concentrations 3.0 mol/L NH4OH+1.5 mol/L
(NH4)2SO4; temperature 25 °C; liquid-to-solid ratio 20 mL/g; (NH4)2SO4; particle size 0.100−0.150 mm; stirring speed
stirring speed 500 r/min) 500 r/min)

sulphate solution. Removal of malachite by dissolution

increases the content of other elements in the ore.
NH4OH+(NH4)2SO4 solution was applied as
leaching medium in these experiments for the dissolution
of malachite ore. The copper extraction rate and pH
value of ammonia leaching medium for the leaching of
malachite are listed in Table 2. When 3 mol/L NH4OH is
used as leaching medium, maximum copper extraction is
only 35% at 180 min (Fig. 3). And when the ammoniacal
reagents (3.0 mol/L NH4OH + 1.5 mol/L (NH4)2SO4
solution) are used, the recovery can reach 87.0% at
120 min. When 13.4 mol/L NH4OH solution is used as
leaching medium, the copper extraction is 73%.
Fig. 6 Effect of liquid-to-solid ratio on copper recovery of
malachite (Ammonia concentration 3.0 mol/L NH4OH + Table 2 Relationship between pH and copper extraction in
1.5 mol/L (NH4)2SO4; temperature 25 °C; particle size 0.100− various ammonia leaching media
0.150 mm; stirring speed 500 r/min; time 180 min) Copper
Leaching medium pH extraction
recovery when liquid-to-solid ratio is over 25 mL/g. rate/%
3.2.6 Effect of temperature 1.0 mol/L NH4OH +1.0 mol/L (NH4)2SO4 8.95 33.0
The effect of reaction temperature on the dissolution 1.0 mol/L NH4OH + 1.5 mol/L (NH4)2SO4 8.78 35.6
of malachite was investigated at 15, 25, 35, 45 and 55 °C. 2.0 mol/L NH4OH + 0.5 mol/L (NH4)2SO4 9.56 64.5
In order to dissolve malachite completely, the liquid-to- 2.0 mol/L NH4OH + 1.0 mol/L (NH4)2SO4 9.16 70.3
solid ratio of 25 mL/g was adopted. As can be seen from
3.0 mol/L NH4OH +0.5 mol/L (NH4)2SO4 9.73 76.1
Fig. 7, the extraction rate of copper increases with the
3.0 mol/L NH4OH +1.0 mol/L (NH4)2SO4 9.43 82.1
increase of temperature. The extraction rate of copper
after 120 min reaches 96.8% and 98.2% for 25 °C and 3.0 mol/L NH4OH +1.5 mol/L (NH4)2SO4 9.16 87.0
55 °C, respectively. But the effect of temperature on the 5.0 mol/L NH4OH +0.5 mol/L (NH4)2SO4 9.96 74.0
copper extraction is insignificant after 90 min of 5.0 mol/L NH4OH +1.0 mol/L (NH4)2SO4 9.65 78.1
leaching. 13.4 mol/L NH4OH 12.53 73.0
Temperature 25 °C; particle size 150−100 µm; liquid-to-solid ratio 20 mL/g;
3.3 Discussion time 120 min.
XRD analyses of the leaching residues show that
malachite is completely dissolved, whereas dolomite and Kinetic evaluation of reactions which appear in the
quartz are not dissolved in the ammonia/ammonium ammonia leaching of malachite illuminates that the
908 J. Cent. South Univ. (2012) 19: 903−910
leaching reactions are confirmed neither with chemical 1
ln(1  x)  [1  (1  x) 1/ 3 ]  k 0 c( NH 3  H 2 O) a 
nor diffusion kinetic models of dissolution. These 3
models are insufficient to account for the reaction of c[( NH 4 ) 2 SO 4 ]b (d p ) c exp[ E/( RT )]t (5)
malachite at the inception of dissolution (i.e. 5−10 min)
and for the total leaching period investigated, because no where T is the temperature, K; c(NH3·H2O) is the
precision curves could be obtained from these two ammonia concentration; c[(NH4)2SO4] is the ammonium
models. A new model, which is based on the interface sulphate concentration; k0 is the apparent reaction rate
transfer and diffusion across the product layer [21], is coefficient; dp is the particle diameter, mm.
enough to explain the ammonia leaching of malachite. For different ammonia concentration, when other
Equation of this model is written as follows: parameters are kept constant, Eq. (5) could be written as
1 1
ln(1  x)  [1  (1  x) 1 / 3 ]  kt (4) ln(1  x)  [1  (1  x) 1/ 3 ]  k1c( NH 3  H 2 O) a t (6)
3 3
where x is the reacted fraction of malachite, k is the rate
1 
constant, and t is the leaching time. d  ln(1  x)  [1  (1  x) 1/ 3 ]
3   k c( NH  H O) a (7)
1
Plot of ln(1  x)  [1  (1  x) 1/ 3 ] versus leaching dt
1 3 2
3
time (t) at different temperatures from Eq. (4) is given in 1 
d  ln(1  x)  [1  (1  x) 1/ 3 ]
Fig. 8(a). Obviously, the model is fitted well to all date  3  is the slope of the
sets. dt
In order to determine the effect of experimental straight line corresponding to different ammonia concen-
variables, including ammonia concentration and 1
tration in Fig. 8(b). Similarly, d{ ln(1  x)  [1  (1 
ammonium sulphate concentration, temperature and 3
particle size (dp) on the dissolution kinetics, the x) 1/ 3 ]}/dt is the slope of the straight line corresponding
following semi-empirical model is established: to ammonium sulphate concentration and particle size in

1
Fig. 8 Plots of ln(1  x)  [1  (1  x) 1/ 3 ] versus time at different operation parameters: (a) Temperature; (b) Ammonia concentration;
3
(c) Ammonium sulphate concentration; (d) particle size
J. Cent. South Univ. (2012) 19: 903−910 909
Figs. 8(c) and (d), respectively. The value of 1
ln(1  x)  [1  (1  x) 1 / 3 ]  kt (9)
ln[d[(1/3)ln(1−x)−[1−(1−x)−1/3]]/dt] versus 3
ln[c(NH3·H2O)] is plotted to get a straight line in Using the fitted k value (Fig. 8(a)), Arrhennius
Fig. 9(a), and the slope is calculated to be 2.983, that is, curve for the dissolution of malachite is shown in Fig. 10.
the value of a is equal to 2.983. Similarly, the value of b The calculated activation energy is 26.75 kJ/mol.
and c could be estimated as 0.941 1 and −0.945 1,
respectively, as given in Fig. 9.

Fig. 10 Arrhenius curve obtained for dissolution of malachite

ore

Substituting the value of a, b c and E into Eq. (5),

and the value of k0 is calculated to be about 72.37 min−1
when the equation fits different straight lines in Fig. 8.
Consequently, the model equation can be expressed as
1
ln(1  x)  [1  (1  x) 1/ 3 ]  72.37  c( NH 3  H 2 O) 2.983 
3
c[( NH 4 ) 2 SO 4 ]0.941 1 (d p ) 0.954 1 exp(3 217.5/T )t

4 Conclusions

1) The dissolution kinetic of malachite in ammonia/

ammonium sulphate solutions is investigated. It is
observed that the main important parameters are
determined as leaching time, ammonia/ammonium
concentration, leaching temperature and particle size.
2) The optimal leaching conditions of malachite ore
are found as ammonia/ammonium sulphate concentrations
are 3.0 mol/L NH4OH + 1.5 mol/L (NH4)2SO4, liquid-to-
solid ratio is 25 mL/g, leaching time is 120 min, leaching
temperature is 25 °C, stirring speed is 500 r/min and
particle size is finer than 45 µm. Under these conditions,
the copper extraction rate could be as high as 96.8%.
3) The dissolution process of malachite was found
to be controlled by mixture kinetics. The reaction rate is
affected by both the interface transfer and diffusion
Fig. 9 Plots of ln[d[1/3ln(1−x)−(1−(1−x)−1/3)]/dt] versus across the product layer. The activation energy was
ln[c(NH3·H2O)] (a), ln[c(NH4)3SO4] (b) and ln dp (c) found to be 26.75 kJ/mol. The model equation can be
expressed as
When the other parameters are fixed with 1
ln(1  x)  [1  (1  x) 1/ 3 ]  72.37  c( NH 3  H 2 O) 2.983 
temperature as the variable factor, the equation can be 3
written as c[( NH 4 ) 2 SO 4 ]0.941 1 (d p ) 0.954 1 exp(3 217.5/T )t
910 J. Cent. South Univ. (2012) 19: 903−910
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