Trans. Nonferrous Met. Soc.

China 22(2012) 2822−2830

Leaching kinetics of low-grade copper ore containing calcium-magnesium

carbonate in ammonia-ammonium sulfate solution with persulfate
LIU Zhi-xiong1, 2, YIN Zhou-lan1, HU Hui-ping1, CHEN Qi-yuan1
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
Received 30 September 2011; accepted 23 December 2011

Abstract: The leaching kinetics of copper from low-grade copper ore was investigated in ammonia-ammonium sulfate solution with
sodium persulfate. The effect parameters of stirring speed, temperature, particle size, concentrations of ammonia, ammonium sulfate
and sodium persulfate were determined. The results show that the leaching rate is nearly independent of agitation above 300 r/min
and increases with the increase of temperature, concentrations of ammonia, ammonium sulfate and sodium persulfate. The EDS
analysis and phase quantitative analysis of the residues indicate that bornite can be dissolved by persulfate oxidization. The leaching
kinetics with activation energy of 22.91 kJ/mol was analyzed by using a new shrinking core model (SCM) in which both the
interfacial transfer and diffusion across the product layer affect the leaching rate. A semi-empirical rate equation was obtained to
describe the leaching process and the empirical reaction orders with respect to the concentrations of ammonia, ammonium sulfate and
sodium persulfate are 0.5, 1.2 and 0.5, respectively.
Key words: low-grade copper ore; calcium-magnesium carbonate; leaching kinetics; ammoniacal solution; sodium persulfate;
activation energy; shrinking cure model

ore, acid medium is not suitable for leaching owing to

1 Introduction the excessive acid consumption. However, ammonia is
an attractive reagent because it does not react with
Copper ore exists mainly in the forms of sulfide and carbonates and siliceous gangue, and then it is ease of
oxidized copper ore, such as chalcopyrite, bornite, purification, low-cost production and amenability to
malachite and chrysocolla. Copper sulfides are generally regeneration.
separated and concentrated from gangue by flotation and The dissolution of covellite was investigated in
treated by conventional pyrometallurgical processes. ammoniacal solutions under the oxygen pressure
Although treatments by pyrometallurgical processes are conditions [17]. It was found that the dissolution kinetics
not attractive on account of large amounts of SO2 was controlled by chemical reaction rate. The ammonia-
produced, approximately 80%−85% of the total metallic oxygen leaching of chalcopyrite in an in-situ
copper is produced pyrometallurgically [1]. However, environment was performed by BELL et al [18]. It could
with gradual depletion of high-grade copper ore deposits, be concluded that the most significant parameters for
it becomes more difficult to extract copper by the chalcopyrite in ammoniacal lixiviants were temperature,
conventional pyrometallurgical methods. Hydro- oxygen pressure and ammonia concentration. Activation
metallurgy is suitable for lean and complex ores, energies were 31.4 kJ/mol and 37.7 kJ/mol for two
especially low-grade ores, waste rocks tailings [2−4], and different chalcopyrite specimens. EKMEKYAPAR et al
results in the increase of metal recoveries and the [19] studied the dissolution kinetics of an oxidized
reduction of air pollution hazard. copper ore containing malachite mainly and covellite
There are many studies related to the leaching of slightly in water saturated by chlorine. It was found that
oxidized and sulfide copper ores in ammoniacal media the dissolution proceeded in two stages and was
[5−13] or acidic media [14−16]. If there is a controlled by diffusion through the ash layer in each
preponderance of carbonates or siliceous gangue in the stage. The dissolution kinetics of copper ore were

Foundation item: Project (2007CB613601) supported by the National Basic Research Program of China; Project (10C1095) supported by the Foundation of
Hunan Educational Committee, China
Corresponding author: YIN Zhou-lan; Tel: +86-731-88877364; E-mail: yzllxh@gmail.com
DOI: 10.1016/S1003-6326(11)61538-0
 LIU Zhi-xiong, et al/Trans. Nonferrous Met. Soc. China 22(2012) 2822−2830 2823
1−3(1−x)2/3−2(1−x)=k1t and 1−3(1−x)2/3−2(1−x)=k2t Table 3, respectively. The phases of copper in the ore
(where x is reaction fraction, k1 and k2 are rate constants, were identified to be malachite mainly, chrysocolla
t is time) for the first and second stages, respectively. The secondly and bornite thirdly, corresponding to free
activation energies were 27.15 kJ/mol (I) and 20.21 copper oxide, copper silicate and second copper sulfide
kJ/mol (II), respectively. (Table 2). The analysis results of element contents by
Tangdan oxidized copper ore, which contains EDS in Table 3 are very close to the theoretical values of
high-grade calcium magnesium carbonate gangues and malachite, chrysocolla and bornite, respectively. Hence,
has poor floatable characteristics, is one of the largest the phases of copper deduced by EDS analysis are the
copper mines in China. Its reserve is about 115×104 t and same as those observed by the polarizing microscope
its average content of copper is 0.75% (mass fraction). method.
LIU et al [12] investigated the dissolution kinetics of
low-grade copper ore in ammonia-ammonium chloride
solution. The results indicate that the malachite is
dissolved easily and chrysocolla is extracted difficultly in
ammoniacal solution and bornite is not dissolved in
ammonia leaching without oxidants. Therefore, it makes
a focus that how to extract bornite in ammoniacal
solution.
Persulfate is known to be a strong oxidant in the
basic solutions and has been used as a leaching agent for
the recovery of metal in alkaline solutions [20,21]. The
dissolution of low-grade copper ore in ammonia-
ammonium sulfate solution with persulfate has not been
reported. Fig. 1 X-ray diffraction pattern of copper ore
In the present study, the effects of concentrations of
ammonia, ammonium sulfate and sodium persulfate, Table 2 Phase composition of oxide copper ore
temperature, particle size and stirring speed on the Relative content
leaching rate of low-grade copper ore in ammonia- Phase w(Cu)/%
of Cu /%
ammonium sulfate solution are interpreted. Free copper oxide 0.383 49.74
Copper silicates 0.220 28.57
2 Experimental Second copper sulfide 0.160 20.78
Primary copper sulfide 0.007 0.91
2.1 Materials Total Cu 0.770 100.00
The oxidized copper ore from Yunnan province in
China was ground into different particle sizes of 0.037, Table 3 Element content of copper ore by EDS (mass fraction
0.045−0.063, 0.074−0.100, 0.150−0.180, 0.250−0.300 %)
mm. The chemical analysis and X-ray diffraction pattern Area in
of the copper ore are given in Table 1 and Fig. 1, Cu Fe S O Si Ca Mg C Cl
Fig. 2
respectively. The content of copper in the ore is too low Area 1 59.89 0.96 29.00 3.89 1.08 5.18
to be detected by X-ray diffraction method. Figure 1 Area 2 45.13 1.60 30.92 21.43 0.71 0.21
indicates that gangue contains muscovite, calcite, Area 3 60.13 10.11 22.08 1.22 1.40 2.94 1.22
dolomite and quartz.
2.2 Leaching procedure
Table 1 Chemical composition of oxidized copper ore (mass The leaching experiments were performed in a 500
fraction, %)
mL reactor with a four-neck split flask in a thermostatic
CuO CaO MgO SiO2 Fe2O3 ZnO Al2O3 K2O Na2O heating mantle. The reactor was equipped with a
0.96 29.00 12.92 25.90 2.84 0.11 1.95 1.35 0.07 condenser, a mercury thermometer, an overhead
mechanical stirrer and a rubber stopper to take samples
The SEM images and corresponding EDS analyses, from the leaching solution. The desired temperature of
the mineralogical composition and the element analysis the flask within ±0.5 °C was adjusted by a
of EDS for the oxidized copper ore with particle size of thermostatically controlled electric heating mantle.
0.045−0.063 mm are presented in Fig. 2, Table 2 and Agitation was provided by a mechanical stirrer. 200 mL
2824 LIU Zhi-xiong, et al/Trans. Nonferrous Met. Soc. China 22(2012) 2822−2830

Fig. 2 SEM images (a,b,c) and corresponding EDS analyses (a′,b′,c′) of copper ore (White parts contain copper minerals)

solution containing specific lixiviant was added into the r/min and the copper dissolution was independent of the
reactor. When the desired stirring speed and reaction agitation over this speed. As a result, agitation speed was
temperature were reached, the solid sample was added maintained at 500 r/min in the subsequent experiments to
into the reactor. 2 mL of sample solution was withdrawn eliminate the effect of agitation as a variable on the
at specific time intervals and filtered for analyzing the leaching rate.
concentration of copper by an atomic absorption
spectrophotometer (AAS). At the same time, 2 mL of 3.1 Effect of temperature
fresh lixiviant was added into the reactor to keep the The effect of temperature on the dissolution of
volume of the solution constant. Filtration was made copper was investigated in the range from 293 to 323 K.
after each leaching experiment. The leached residue was The results are given in Fig. 3. It can be observed that the
weighed after being dried at 110 °C for 8 h. extraction of copper increases with the increase of
leaching time at different temperatures. The copper
3 Results and discussion dissolution rate is greatly affected by temperature. When
the temperature ranges from 293 to 323 K, the extraction
The effect of agitation speed on the copper leaching of copper is increased from 30.2% to 50.1% after 2 min.
was carried out in the range from 100 to 500 r/min. An The extraction of copper after 60 min reaches 80 % at
adequate suspension of the solid was observed at 300 293 K and 89.4 % at 323K, respectively.
 LIU Zhi-xiong, et al/Trans. Nonferrous Met. Soc. China 22(2012) 2822−2830 2825
extraction of copper increases with the increase of
ammonia concentration when more reaction molecules
can attack the solid.
The effect of ammonium sulfate concentration on
the dissolution of copper was investigated at 2.5 mol/L
ammonia as shown in Fig. 4(b). It illustrates that the
leaching rate increases when the concentration of
ammonium sulfate increases.

3.3 Effect of sodium persulfate concentration

Figure 5 shows the effect of sodium persulfate
concentration on the leaching rate of copper at 303 K. It
shows that the extraction of copper increases with the
Fig. 3 Effect of temperature on extraction of copper (2.5 mol/L increase of sodium persulfate concentration in the range
ammonia, 2.0 mol/L ammonium sulfate, 0.05 mol/L sodium assessed. At the initial time of leaching, the extraction of
persulfate, stirring speed 500 r/min, liquid-to-solid ratio 40 copper increases greatly. The extraction of copper
mL/g and particle size 0.045−0.063 mm) reaches 86.2% and 87.6% when the concentrations of
persulfate are 0.050 and 0.075 mol/L at 60 min,
3.2 Effect of ammonia and ammonium sulfate respectively. And then there is no significant increase for
concentration the extraction of copper.
Experiments on the dissolution of the copper ore
were performed to investigate the effect of ammonia
concentration at 2.0 mol/L ammonium sulfate. The
results are shown in Fig. 4(a). It is indicated that the

Fig. 5 Effect of sodium persulfate concentration on extraction

of copper (Temperature 303K, 2.5 mol/L ammonia, 2.0 mol/L
ammonium sulfate, stirring speed 500 r/min, liquid-to-solid
ratio 40 mL/g and particle size 0.045−0.063 mm)

3.4 Effect of particle size

Experiments were performed to investigate the
effects of particle sizes on the dissolution behavior of
copper. The results are presented in Fig. 6. As expected,
the smaller the size of the particles, the faster the
dissolution rate. It is possibly attributed to the active sties
of the copper ores on the surface of particles in the
dissolution. When the specific size gets smaller, more
active sites on the solid surface are exposed to the
solution. As the leaching proceeds, the reactants
penetrate into the micro-cracks and more soluble forms
Fig. 4 Effect of concentrations of ammonia (a) and ammonium of copper are extracted.
sulfate (b) on extraction of copper (Temperature 303 K, 0.05
mol/L sodium persulfate, stirring speed 500 r/min, liquid-to- 3.5 Effect of liquid-to-solid ratio
solid ratio 40 mL/g and particle size 0.045−0.063 mm) The effect of liquid-to-solid ratio range on the
2826 LIU Zhi-xiong, et al/Trans. Nonferrous Met. Soc. China 22(2012) 2822−2830
leaching of low grade oxidized copper ore was ammonia-oxygen solution.
investigated from 10 to 50 mL/g at 303 K. The results FURMAN et al [23] proposed the decomposition
are given in Fig. 7. It indicates that the increase of mechanism of persulfate in alkaline solution as follows:
liquid-to-solid ratio can enhance the leaching of copper. 2S2O82−+2H2O ⎯OH
−
⎯⎯→ 4SO42−+O2+4H+ (3)
But there is no significant change on the extraction of
copper when liquid-to-solid ratio increases. This can be Equation (3) indicates that the reaction of S2O82−
explained that the lixiviant is excess of the calculated with ammonia may take place as follows:
amount for the extraction of copper. 2S2O82−+4NH3+2H2O=4SO42−+O2+4NH4+ (4)
The dissolution of bornite in ammonia-oxygen
system may occur according to the following reaction:
2Cu5FeS4+18.5O2+36NH3+H2O+2(NH4)2SO=
10Cu(NH3)42++2Fe(OH)3+10 SO42− (5)
Summing reactions Eq. (4) and Eq. (5) provides the
following net reaction for the leaching of bornite in
ammonia-ammonium sulfate with persulfate:
Cu5FeS4+18.5S2O82−+55NH3+19H2O=
5Cu(NH3)42++Fe(OH)3+41SO42-+35NH4+ (6)
Equation (1) indicates that malachite can be
dissolved, Eq. (2) indicates that chrysocolla may be
Fig. 6 Effect of particle size on extraction of copper dissolved difficultly owing to the absorption of silica on
(Temperature 303 K, 2.5 mol/L ammonia, 2.0 mol/L the surface of the solid, and Eq. (3) indicates that bornite
ammonium sulfate, 0.05 mol/L sodium persulfate, may be dissolved by oxidation of persulfate.
liquid-to-solid ratio 40 mL/g, stirring speed 500 r/min) The SEM images of the leaching residues and the
element analysis of the EDS are shown in Fig. 8 and
Table 4, respectively. The micrographs of the solid
particles before leaching present a rough and porous
surface as observed in Fig. 2. However, the micrographs
of the leaching residues present different surfaces.
Malachite was almost dissolved and could not be
observed in the leaching residue by EDS. Figure 8(a′)
and Table 4 indicate that chrysocolla is dissolved partly
compared with Fig. 2(b′). Figure 8(a) shows that the
morphology of the undissolved and partially dissolved
chrysocolla is a little bit more rough and porous than that
of chrysocolla before leaching (Fig. 2(b)). During the
leaching, the precipitated silica is absorbed on the
Fig. 7 Effect of liquid-to-solid ratio on extraction of copper
surface of the particle of chrysocolla as observed in Fig.
(Temperature 303 K, 2.5 mol/L ammonia, 2.0 mol/L
8(a), which may block the surface-active sites of the
ammonium sulfate, 0.05 mol/L sodium persulfate, leaching
copper ores and reduce the reactivity. Figure 8(b′) shows
time 120 min, stirring speed 500 r/min, and particle size
that bornite can be mostly oxidized with persulfate
0.045−0.063 mm)
compared with Fig. 2(c′). As seen from Fig 8(b), the
morphology of the residue derived from the oxidization
3.6 Dissolution mechanism and residue analysis
of bornite is different from that of the ore before leaching
Malachite and chrysocolla in ammoniacal solution
and presents a rough and porous surface which is of
take place according to Eq. (1) and Eq. (2), respectively:
needle-shape to a certain extent. The phases of copper in
Cu2(OH)2CO3+6NH4OH+2(NH4)2SO4= the ore before and after leaching are listed in Table 5. It
2Cu(NH3)42++2SO42−+CO32−+2NH4++8H2O (1) confirms that bornite can be oxidized and dissolved by
CuSiO3⋅H2O+2NH4OH+(NH4)2SO4= persulfate in the ammonia-ammonium sulfate solution.
Cu(NH3)42++SO42−+SiO2↓+4H2O (2)
PARK et al [22] and REILLY and SCOTT [17] 3.7 Kinetics analysis
drew the similar conclusion that S2− in the sulphide The shrinking core model (SCM) considers that the
minerals is eventually oxidized into SO42− in rate of controlling step of dissolution process is either the
 LIU Zhi-xiong, et al/Trans. Nonferrous Met. Soc. China 22(2012) 2822−2830 2827

Fig. 8 SEM images (a,b) and EDS analyses (a′,b′) of leaching residue (The white parts contain copper minerals)

Table 4 EDS analysis for leaching residue (mass fraction %) integrated equation of the shrinking core model can be
Area Cu Fe S O Si Ca Mg C Al given as [24]
4 32.08 1.37 0.54 23.43 14.51 4.96 2.82 17.96 0.59 1−(1−x)1/3=krt (8)
5 2.63 49.80 8.07 7.48 3.86 8.07 1.57 0.67
where x is reaction fraction, kd and kr are rate constants,
and t is reaction time.
Table 5 Phase of copper in copper ore before and after leaching According to Eq. (7) and Eq. (8), when the process
Relative content of is controlled by diffusion through a solid product layer,
w(Cu)/%
Cu /%
Phase the plot of 1−(2/3)x−(1−x)2/3 versus time is a straight line
Before After Before After
with a slope kd, similarly, when the process is chemically
leaching leaching leaching leaching
controlled, the plot of 1−(1−x)1/3 versus time is also a
Free copper oxide 0.383 49.74
straight line with a slope kr. Equations (7) and (8) are
Copper silicates 0.220 0.101 28.57 93.52 often used to describe the leaching process when it is
Second copper controlled by diffusion through a solid product layer or
0.007 0.003 0.91 2.78
sulfide
by chemical reaction.
Primary copper
0.160 0.004 20.78 3.70 For the kinetics analysis in the present work, the
sulfide
shrinking core models with diffusion through product
Total Cu 0.770 0.108 100 100
layer and surface chemical reaction, Eq. (7) and Eq. (8)
were evaluated. The left sides of these expressions were
diffusion through solution boundary, or the diffusion
plotted with respect to the leaching time, and then the
through a solid product layer, or the surface chemical
correlation of the kinetics data with these models was
reaction. Assuming that the copper particles have a
assessed by using correlation coefficient (R2) values in
spherical geometry and the process is controlled by
diffusion through production layer, the integrated Table 6. The slopes of these plots are the apparent rate
equation of the shrinking core model can be expressed as constants (kd and kr).
[24] Although the dissolution-controlled model Eq. (7)
fitted better compared with the chemically controlled
1−(2/3)x−(1−x)2/3=kdt (7) model Eq. (8), the SCM with diffusion-controlling is not
When the process is chemically controlled, the well fitted with the experimental data. The correlation
2828 LIU Zhi-xiong, et al/Trans. Nonferrous Met. Soc. China 22(2012) 2822−2830
2
coefficients (R ) for diffusion control and chemical
control were both below 0.84. Hence, a new SCM
proposed by DICKNSON and HEAL [25] was applied to
describing the dissolution process. This model is based
on the assumption that both the interface transfer and
diffusion across the product layer affect the leaching rate.
Equation of this model is written as follows:
(1/3)ln(1−x)+(1−x)−1/3−1=kt (9)
The results of the kinetics analysis including the
correlation coefficient when the leaching data were fitted
to Eq. (9) are shown in Table 6. As can be seen from
Table 6, the model Eq. (9) fits the best in all the
experiments. Therefore, model of Eq. (9) was adopted to
Fig. 10 Arrhenius plot of copper dissolution of oxidized copper
describe the dissolution of copper in ammonia-
ore
ammonium sulfate solution with persulfate. Figure 9
presents a good fit (R2>0.9455) by plotting
(1/3)ln(1−x)+(1−x)−1/3−1 versus time at different
temperatures.

Table 6 Correlation coefficients (R2) of three kinetics models at

different temperatures
R2
T/K
1−(1−x)1/3 1−(2/3)x−(1−x)2/3 (1/3)ln(1−x)+(1−x) −1/3−1
293 0.6258 0.8017 0.9455
303 0.5939 0.7769 0.9475
313 0.6645 0.8301 0.9736
323 0.5694 0.7395 0.9468

The Arrhenius plot constructed with the rate

constant value (k), which is calculated from the data
given in Fig. 9, is presented in Fig. 10. The calculated
activation energy (Ea) for the dissolution of the oxidized
copper ore is 22.91 kJ/mol.

Fig. 9 Plots of 1/3ln(1−x)+(1−x)−1/3−1 versus time at different

temperatures

A serious well-fitted plots of (1/3)ln(1−x)+

(1−x)−1/3−1 versus time at different concentrations of Fig. 11 Plots of (1/3)ln(1−x)+(1−x)−1/3−1 versus time at
ammonia, ammonium sulfate and sodium persulfate are different concentrations of ammonia, ammonium sulfate and
given in Fig. 11. From the slops of the straight lines in sodium persulfate
 LIU Zhi-xiong, et al/Trans. Nonferrous Met. Soc. China 22(2012) 2822−2830 2829
Fig. 11(a), the apparent rate constant (k) was determined ammonium sulfate and sodium persulfate were applied to
and lnk versus ln[NH3H2O] plot (Fig. 12(a)) was developing the kinetics model. The rate constant of the
constructed to determine the order of dependency with new SCM model is directly proportional to the
respect to ammonia concentration. The empirical concentration of liquid reactant, and the effects of all the
reaction order for ammonia concentration is 0.5. In a factors on the rate constant can be expressed as follows:
similar way, the empirical reaction orders obtained for
k=k0[NH3H2O]a·[(NH4)2SO4]b·[Na2S2O8]ce−Ea/(RT) (10)
ammonium sulfate and sodium persulfate concentrations
are 1.2 and 0.5, respectively (Fig. 12). Comparing Eq. (9) with Eq. (10), the dissolution
The control parameters used in the present work, kinetics of low-grade copper ore can be expressed as
including temperature, concentrations of ammonia, follows:
(1/3)ln(1−x)+(1−x)−1/3−1=k0[NH3H2O]a·
[(NH4)2SO4]b·[Na2S2O8]ce−Ea/(RT)t (11)
where k0 is constant and Ea is the activation energy of the
dissolution process. k0 is calculated to be 53.46 min−1
according to the intercept of the straight lines in Fig. 9.
Consequently, the following kinetics expression can be
used to describe the dissolution of copper from the
low-grade copper ore:
(1/3)ln(1−x)+(1−x)−1/3−1=53.46[NH3H2O]0.5·
[(NH4)2SO4]1.2·[Na2S2O8]0.5e−22910/(RT)t (12)

4 Conclusions

1) The dissolution kinetics of copper from

low-grade oxidized copper ore was investigated in
ammonia-ammonium sulfate solution with sodium
persulfate. It was found that agitation speed above 300
r/min is sufficient to eliminate the effect of agitation as a
variable on the leaching rate. The extraction of copper is
increased with the increase of reaction temperature,
concentrations of ammonia, ammonium sulfate and
sodium persulfate and with the decrease of particle size.
2) A new shrinking core model, which is based on
the interfacial transfer and diffusion through the product
layer, can be well used to describe the dissolution
kinetics of copper in the ammonia- ammonium sulfate
solution. The semi-empirical kinetics equation of the
dissolution of copper can be expressed as Eq. (12). The
activation energy was found to be 22.91 kJ/mol and the
empirical reaction orders with respect to the
concentrations of ammonia, ammonium sulfate and
sodium persulfate were determined to be 0.5, 1.2 and 0.5,
respectively.
3) The EDS and phase analyses of the residues
indicate that malachite is dissolved completely, bornite is
extracted by persulfate oxidization and chrysocolla can
be partly dissolved in ammonia- ammonium sulfate
solution.

Fig. 12 Plots of ln{d[(1/3)ln(1−x)+(1−x)−1/3−1]} versus

References
ln{[NH3H2O]/(mol·L)}, ln{[(NH4)2SO4]/(mol·L)} and
ln{[Na2S2O8]/(mol·L)}: (a) Ammonium; (b) Ammonium sulfate; [1] ANTONIJEVIĆ M M, JANKOVIĆ Z D, DIMITRIJEVIĆ M D.
(c) Sodium persulfate Kinetics of chalcopyrite dissolution by hydrogen peroxide in
2830 LIU Zhi-xiong, et al/Trans. Nonferrous Met. Soc. China 22(2012) 2822−2830
sulphuric acid [J]. Hydrometallurgy, 2004, 71(3−4): 329−334. [13] OUDENNE, P D, OLSON F A. Leaching kinetics of malachite in
[2] WALTING H R. The bioleaching of sulphide minerals with emphasis ammonium carbonate solutions [J]. Metallurgical Transactions B,
on copper sulphide—A review [J]. Hydrometallurgy, 2006, 84(1−2): 1983, 14(1): 33−40.
81−108. [14] BINGŐL D, CANBAZOĞLU M. Dissolution kinetics of malachite
[3] WU Heng-shan, LIU Yong. Study on copper recovery from tailing by in sulphuric acid [J]. Hydrometallurgy, 2004, 72(1−2): 159−165.
means of leaching progress [J]. China Mining Magazine, 2001, 10(6): [15] SOKIĆ M D, MARKIVIĆ B, ŽIVKOVIĆ D. Kinetics of
65−67. (in Chinese) chalcopyrite leaching by sodium nitrate in sulphuric acid [J].
[4] ZHAO Guo-dong, WU Heng-shan, ZHANG Yu, LIU Qing. Hydrometallurgy, 2009, 95(3−4): 273−279.
Ammonia leaching for tailings from a copper mine [J]. Nonferrous [16] ADEBAYO A O, IPINMOROTI K O, AJAYI O O. Dissolution
Metals, 2004, 56(3): 54−56. (in Chinese) kinetics of chalcopyrite with hydrogen peroxide in sulphuric acid
[5] KÜNKÜL A, KOCAKERIM M M, YAPICI S, DEMIRBAǦ A. medium [J]. Chem Biochem Eng, 2003, 17(3): 213−218.
Leaching kinetics of malachite in ammonia solutions [J]. [17] REILLY I G, SCOTT D S. The leaching of cupric sulfide in
International Journal of Mineral Processing, 1994, 41(3−4): ammonia [J]. Ind Eng Chem Process Des Dev, 1976, 15(1): 60−67.
167−182. [18] BELL S L, WELCH G D, BENNETT P G. Development of
[6] WANG Xi, CHEN Qi-yuan, HU Hui-ping, YIN Zhou-lan, XIAO ammoniacal lixiviants for the in-situ leaching of chalcopyrite [J].
Zhong-liang. Solubility prediction of malachite in aqueous Hydrometallurgy, 1995, 39(1−3): 11−23.
ammoniacal ammonium chloride solutions at 25 °C [J]. [19] EKMEKYAPARS A, COLAK S, ALKAN M. Dissolution kinetics
Hydrometallurgy, 2009, 99(3−4): 231−237. of an oxidized copper ore in water saturated by chlorine [J]. Journal
[7] DEMIRKIRAN N, EKMEKYAPAR A, KÜNKÜL A, BAYSAR A. of Chemical Technology and Biotechnology, 1988, 43(3): 195−204.
A kinetic study of copper cementation with zinc in aqueous solutions [20] LI Dun-fang, WANG Cheng-yan, YIN Fei, CHEN Ying-qiang, JIE
[J]. Inter J Miner Proc, 2007, 82(2): 80−85. Xiao-wu. Effect of additive on copper removal from spent
[8] ÇALBAN T, ÇOLAK S, YEŞILYURT M. Optimization of leaching lithium-ion batteries by ammoniacal leaching [J]. Chinese Journal of
of copper from oxidized copper ore in NH3-(NH4)2SO4 medium [J]. Power Sources, 2009, 33(6): 454−457. (in Chinese)
Chemical Engineering Communications, 2005, 192(10−12): [21] REED W A, GARNOV Y A, RAO L, NASH K L, BOND A H.
1515−1524. Oxidative alkaline leaching of Americium from simulated high-level
[9] BINGÖL D, CANBAZOĞLU M, AYDOĞAN S. Dissolution nuclear waste sludges [J]. Separation Science and Technology, 2005,
kinetics of malachite in ammonia/ammonium carbonate leaching [J]. 40(5):1029−1046.
Hydrometallurgy, 2005, 76(1−2): 55−62. [22] PARK K H, MOHAPATRA D, REDDY B R, NAM C W. A study
[10] ARZUTUG M E, KOCAKERIM M M, COPUR M. Leaching of mal on the oxidative ammonia- ammonium sulfate leaching of a complex
achite ore in NH3-saturated water [J]. Ind Eng Chem Res, 2004, (Cu−Ni−Co−Fe) matte [J]. Hydrometallurgy, 2007, 86(3−4):
43(15): 4118−4123. 164−171.
[11] EKMEKYAPAR A, OYA R, KÜNKÜL A. Dissolution kinetics of an [23] FURMAN O S, TEEL A L, WATTS R J. Mechanism of base
oxidized copper ore in ammonium chloride solution [J]. Chem activation of persulfate [J].Environment Science and Technology,
Biochem Eng Q, 2003, 17(4): 261−266. 2010, 44(16): 6423−6428.
[12] LIU Wei, TANG Mo-tang, TANG Chao-bo. Dissolution kinetics of [24] LEVENSPIEL O. Chemical reaction engineering [M]. New York:
low grade complex copper ore in ammonia-ammonium chloride Wiley, 1972: 361−371.
solution [J]. Transactions of Nonferrous Metals Society of China, [25] DICKINSON C F, HEAL G R. Solid-liquid diffusion controlled rate
2010, 20(5): 910−917. equations [J]. Thermochimica Acta, 1999, 340−341: 89−103.

氨−硫酸铵体系过硫酸盐氧化含钙镁碳酸盐
低品位铜矿的浸出动力学
刘志雄 1, 2，尹周澜 1，胡慧萍 1，陈启元 1

1. 中南大学 化学化工学院，长沙 410083；

2. 吉首大学 化学化工学院，吉首 416000

摘 要：研究在氨−硫酸铵体系中用过硫酸盐氧化低品位铜矿浸出动力学，确定搅拌速度、浸出温度、矿物粒度
及氨、硫酸铵和过硫酸钠的浓度对浸出的影响。结果表明，搅拌速度在 300 r/min 以上时对浸出速度无影响，浸
出速度随反应温度及氨、硫酸铵和过硫酸钠浓度的增大而增加。对浸出渣的 EDS 和物相定量分析表明斑铜矿被
过硫酸盐氧化而溶解于氨−硫酸铵溶液。用产物层的界面传质和扩散控制的收缩核模型分析铜矿的溶解动力学，
其表观活化能为 22.91 kJ/mol，同时获得了描述浸出过程的半经验动力学方程，其对氨、硫酸铵和过硫酸钠的浓
度的表观反应级数分别为 0.5、1.2 和 0.5。
关键词：低品位复杂铜矿；钙−镁碳酸盐；氧化浸出；浸出动力学；氨−硫酸铵；过硫酸钠；活化能；收缩核模型
(Edited by LI Xiang-qun)