Advanced Powder Technology 33 (2022) 103547

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Advanced Powder Technology

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Original Research Paper

Eco-friendly oxidation leaching from chalcopyrite powder and kinetics

assisted by sodium chloride in organic acid media
Hao Chen a,b, Jingfeng He a,b,c,d,⇑, Lingtao Zhu a,b, Bin Liu a,b, Kui Zhou a,b, Jiang Xu a,b, Chengjing Guo a,b
a
School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou 221116, China
b
Key Laboratory of Coal Processing and Efficient Utilization of Ministry of Education, China University of Mining and Technology, Xuzhou 221116, China
c
State Key Laboratory of Mineral Processing Science and Technology, Beijing Mining and Metallurgical Technology Group Co., Ltd., Beijing 100160, China
d
National & Local Joint Engineering Research Center for Deep Utilization of Mineral-salt Resources, Huaiyin Institute of Technology, Huaian 223003, China

a r t i c l e i n f o a b s t r a c t

Article history: The realization of efficient leaching of metal elements in chalcopyrite is of great significance to global
Received 12 November 2021 industrial development. In this work, an eco-friendly and efficient leaching process was investigated
Received in revised form 24 February 2022 for the leaching of Cu and Fe from chalcopyrite powder. The results showed that the introduction of stir-
Accepted 28 March 2022
ring energy has an adverse effect on the leaching process. 96.13% Cu and 84.35% Fe were leached under
Available online 12 April 2022
the optimal leaching conditions of 0 rpm stirring speed, the solid–liquid ratio of 10 g/L, 0.5 M HAc, 0.4 M
NaCl, at 333.15 K for 10 h with timeic addition of H2O2 of 16 mL every 2 h. The kinetics data indicated that
Keywords:
the leaching of Cu fitted best to the shrinking core model while the leaching of Fe corresponded to the
Chalcopyrite powder
Eco-friendly
Avrami equation. Furthermore, all the leaching processes mainly depended on the controlling of diffu-
Sodium chloride sion, and reaction order revealed that the volume of H2O2 had the greatest effect on the leaching rates.
Optimization Ó 2022 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Leaching kinetics Technology Japan. All rights reserved.

1. Introduction +0.4 V is required to leach metal from chalcopyrite according to

Chalcopyrite (CuFeS2), as the principal deposit of low-grade
copper ore, its promising industrial potential is evidenced due to
the possession of about 70% of the world’s copper reserves [1].
Pyrometallurgy is not suitable for large-scale industrial processing
of low-grade copper ore because of its high energy consumption.
Recently, the treatment of chalcopyrite by hydrometallurgy has
been received great attention [2]. Compared with pyrometallurgy,
hydrometallurgy is easier to control waste in the metallurgical pro-
cess, which is beneficial to the protection of ecology and the envi-
ronment [3].
The kinetics and mechanism of chalcopyrite leaching in various
media have always been the focus of researchers [4]. A fundamen-
tal understanding of this phenomenon will help solve the problems
that challenge the implementation of hydrometallurgical pro-
cesses. It is worth noting that the leaching of chalcopyrite is the
most complicated in the hydrometallurgical process. The chalcopy-
rite will be converted into various intermediates through solids in
an acidic aqueous medium during oxidative leaching [5]. In fact, a
pH lower than 4 and an oxidizing redox potential higher than
⇑ Corresponding author at: School of Chemical Engineering and Technology,
China University of Mining and Technology, Xuzhou 221116, China.
E-mail address: jfhe@cumt.edu.cn (J. He).
the Pourbaix diagram of the CuFeS2–H2O system [6]. Hydrogen
peroxide (H2O2) is an eco-friendly oxidizing agent. Besides, its high
oxidation–reduction potential (1.77 V, vs SHE) has also made this
reagent extensively investigated in the oxidation processes of
almost all sulfide minerals [7,8].
However, the formation of the low activity passivation layer is
inevitable under acid oxidation conditions [9]. which hinders the
further progress of leaching. After a long debate, researchers gener-
ally believe that the passivation layer is Cu polysulfide lacking
metal, which is produced by the solid-state transformation of chal-
copyrite surface in the oxidation reaction [10]. Researches indicate
that the presence of chloride ions can change the formation struc-
ture of the passivation layer, thereby improving the leaching per-
formance of chalcopyrite. In addition, this improvement is due to
the following reasons: (1) the formation of metal-chloride com-
plexes; (2) the increase in electrochemical current during the
leaching of chalcopyrite; (3) linear leaching trend [11]. Considering
that new impurities cannot be introduced and economic benefits,
NaCl seems to be the best choice for introducing Cl
ions.
Nowadays, the use of mineral acids (sulphuric acid, nitric acid
and (or) hydrochloric acid) are being applied for leaching metals
from chalcopyrite, and overall performance is also impressive
[12–14]. At the same time, these reagents do produce
hazardous/toxic gases to the environment during leaching and

https://doi.org/10.1016/j.apt.2022.103547
0921-8831/Ó 2022 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.
H. Chen, J. He, L. Zhu et al. Advanced Powder Technology 33 (2022) 103547

the waste liquid treated by these mineral acids needs specific

treatment [15].
Organic acids containing carboxyl functional groups have been
proved to be effective in avoiding these defects. Oxalic acid and
glycine were used to explore the leaching of metals in chalcopyrite
[16,17]. However, the slow leaching rates and strict reaction condi-
tions limit the expansion of the leaching scale. As a low molecular
weight organic acid, acetic acid (HAc) is inexpensive and eco-
friendly, making it an ideal leaching acid agent. In addition, HAc
as a polar organic solvent can effectively inhibit the decomposition
of H2O2 [18]. HAc has successfully achieved the leaching of cal-
cined magnesite, galena and blended copper slag, which proved
that most of the by-products are the same as other acid leaching
[19–21]. Compared with other organic acids, acetic acid has several
advantages including ease of degradable properties under aerobic
and anaerobic conditions, less emission of hazardous gases, and
low acquisition costs [22].
In general, the current process can obtain close to 100% leaching Fig. 1. Particle size distribution of chalcopyrite powder.
efficiency for chalcopyrite, but it takes a high capital cost and a
long leaching time. It is necessary to explore new methods to
improve the leaching efficiency of chalcopyrite and carry out fur-
ther application on a laboratory scale. The HAc-H2O2-NaCl system
can ensure production and environmental safety, and improve the
leaching efficiency without complex pretreatment or addition of
other minerals. Considering that the mechanism of the leaching
of chalcopyrite in similar systems is still unclear, there is no exact
report on the leaching of chalcopyrite with H2O2 in acetic acid.
Therefore, the leaching behavior of chalcopyrite in the HAc-H2O2-
NaCl system was studied. The influence of stirring speed, solid–liq-
uid ratio, sodium chloride concentration and other parameters on
the leaching of chalcopyrite was investigated and the leaching con-
ditions of chalcopyrite were optimized in this system through a
single-factor test. The kinetics of the optimal leaching process from
the chalcopyrite powder were also evaluated with the Avrami
equation and the shrinking core model. The reaction orders of dif-
ferent parameters were obtained by different kinetic models, and
the effect of different parameters on the leaching performance
was compared. This work aims to optimize the parameters and
investigate the dynamics of this eco-friendly method for Fig. 2. XRD analysis results of chalcopyrite powder.

laboratory-scale leaching of chalcopyrite powder.

23.61%, 22.68%, 21.80%, respectively. In addition, the impurity ele-

2. Materials and methods ments of Si, Ca, Zn, Mg exceeded 1%.

2.1. Sample preparation 2.2. Experimental procedures

The raw chunk chalcopyrite sample used in this experiment
was obtained from Hubei, China. In order to minimize the impact
of particle size distribution on the reaction kinetics, a shear crusher
and a standard set of sieves were used to crush the chalcopyrite
sample in a closed circuit to obtain
74 lm chalcopyrite powder.
Particle size analysis is carried by Laser Diffraction Particle Size
Analyzer (LDPSA, Beckman Coulter LS13320XR, America), which
is shown in Fig. 1. According to the particle size distribution
results, it was determined that the particle sizes of the chalcopyrite
powder were as d(10) = 13.77 lm, d(50) = 46.65 lm, d(90) =
67.03 lm. Besides, a small part of the particle size exceeded
74 lm, which was caused by agglomeration between particles.
The crystalline phases of the chalcopyrite powder are identified
using XRD (Bruker D8 Advance, Germany), which is shown in
Fig. 2. The chalcopyrite powder was mainly composed of chalcopy-
rite, bornite, hemimorphite, sinnerite, zircon, etc. The chemical
composition and major elements of the respective sample were
analyzed by X-Ray Fluorescence (XRF, Bruker S8 Tiger, Germany).
The obtained results were visualized in Table 1, Cu, Fe and S were
mainly found in the chalcopyrite powder, which accounted for
2
2.2.1. Leaching
The leaching test was carried out in a 250 mL Erlenmeyer flask,
and the temperature was controlled by a thermocouple in a con-
stant temperature water bath. The stirring of the leaching solution
was provided by a two-blade paddle made of poly tetra fluo-
roethylene (PTFE). The stirring speed and time were controlled
by the controller connected to the stirring motor. Put the chalcopy-
rite powder, HAc solution, and H2O2 (30%, AR) into a 250 mL Erlen-
meyer flask in turn, quickly heated and then the stirring process
was started when the required temperature was reached. Chal-
copyrite is generally considered to be a mineral in Cu+Fe3+(S2-)2,
the dominant reaction equation of chalcopyrite powder in the solu-
tion system is shown in Eq. (1) [23]:
2CuFeS2 þ 17H2 O2 þ 2Hþ ¼ 2Cu2þ þ 2Fe3þ þ SO2

4 þ 18H 2 O ð1Þ
However, specific temperature conditions promote the elemen-
tal sulfur formation and acid consumption (Eq. (2)) [24]:
2CuFeS2 þ 5H2 O2 þ 10Hþ ¼ 2Cu2þ þ 2Fe3þ þ S0 þ 10H2 O ð2Þ
H. Chen, J. He, L. Zhu et al.
Table 1
The XRF results of chalcopyrite powder.
Composition Cu Fe S CO2 Si Ca
Content (%) 23.61 22.68 21.80 18.90 5.37 2.90
The leaching residues after oxidation were washed with deion-
ized water, dried and the content of metal in the leaching residue
was examined by XRF analysis. In the leaching test, all of the
reagents used were analytical purity, and the solvent in the solu-
tion was deionized water. In addition, due to the high temperature
and the presence of metal ions, a large amount of H2O2 was
destroyed instead of participating in the leaching process [25].
Therefore, H2O2 was timeically added to the leaching solution to
enhance the overall leaching performance.
2.2.2. Indicators
In this experiment, the leaching rate (LR) of Cu and Fe from
chalcopyrite powder was based on the XRF test results of the leach-
ing residue, the specific calculation formula is shown in Eq. (3).
m2  a2
LR ¼ 1
 100%
m1  a1
where m1 refers to the weight of chalcopyrite powder before leach-
ing, g; a1 refers to the metal content of chalcopyrite powder before
leaching, %; m2 refers to the weight of residue, g; a2 refers to the
metal content of residue, %.
3. Results and discussion
3.1. Leaching studies
More than one of the factors may affect the overall low leaching
rate of chalcopyrite powder. Therefore, under the operating condi-
tions used in hydrometallurgy, determining the influence of each
factor on the dissolution of minerals was important. The normal
pressure was kept at 1 bar, the leaching behavior of chalcopyrite
powder was studied at 0–10 h, and the result recording interval
was two hours. The variable leaching parameters were stirring
speed (0–400 rpm), solid–liquid ratio (5–25 g/L), HAc concentra-
tion (0.3–0.7 M), NaCl concentration (0–0.8 M), H2O2 volume
(4–20 mL), leaching temperature (303.15–343.15 K).
3.1.1. Effect of stirring speed
The leaching of chalcopyrite powder was a multiphase reaction,
including the mass transfer of reactants to the surface of chalcopy-
rite powder, and the mass transfer of Cu and Fe from the surface of
the chalcopyrite powder to the bulk solution. Therefore, useful
kinetics information about the leaching process can be obtained
by analysing the impact of different stirring speeds on metal leach-
ing efficiency [26]. Fig. 3 shows the effect of stirring speed on the
metal leaching efficiency with the solid–liquid ratio of 15 g/L,
0.6 M HAc, 0.2 M NaCl, at 323.15 K with timeic addition of H2O2
of 12 mL every 2 h. As shown in Fig. 3(a), the LR of Cu continuously
increases with the leaching time. Notably, the LR of Cu gradually
decreased with the increase of the stirring speed with
0–400 rpm. The optimum leaching efficiency of Cu was obtained
when stirring speed was 0 rpm (i.e. heap leaching), and the LR of
Cu reached the maximum value of 72.43% in 10 h. The same results
are found in Fig. 3(b). When there was no stirring, the LR of Fe
reached the maximum value of 63.17%. In addition, LR had not a
simple linear relationship with the leaching time, the LR of Cu
and Fe tended to be stable with the continuous increase of the
leaching time. This phenomenon was more pronounced for high
stirring speed (400 rpm). Therefore, the reaction of chalcopyrite
Advanced Powder Technology 33 (2022) 103547
Zn Mg Pb Al Er Sr Mn Cr As
2.08 1.63 0.38 0.22 0.22 0.15 0.03 0.03 0.01
powder in this system was not controlled by liquid phase diffusion,
and no extra stirring was needed to improve the reaction
efficiency.
The introduction of mechanical stirring is to improve the leach-
ing performance of minerals by adding energy [27]. Mechanical
stirring provided sufficient mass transfer that facilitated the leach-
ing process. Therefore, the leaching performance of the target ele-
ment can be optimized in some leaching processes [28]. However,
stirring is only necessary for particle suspension and gas transfer
[29]. As mentioned in Section 2.2.1, the self-decomposition of
H2O2 was affected by the ionic composition of the solution. As
the leaching reaction progresses, the content of metal ions in the
solution continued to increase. Mechanical stirring improved the
catalytic efficiency of H2O2 by these metal ions, accelerates the
process of self-decomposition, and worsened the leaching perfor-
ð3Þ mance [24]. This also explained that the improvement of the leach-
ing performance by timeic addition of H2O2 will be weakened with
the extension of the leaching time. Besides, The presence of
mechanical agitation also enhances the volatilization of HAc and
the formation of molecular O2 [30]. As a result, more bubbles were
adsorbed on the surface of the chalcopyrite powder, which hin-
dered the contact between the chalcopyrite powder and the solu-
tion [31]. Therefore, effective leaching performance can be
achieved without mechanically stirring. To reduce unnecessary
energy consumption and optimize the leaching conditions, subse-
quent tests will no longer involve mechanically stirring.
3.1.2. Effect of solid–liquid ratio
An appropriate solid–liquid ratio was important for industrial
application design because it determined the energy consumption
before leaching, reactor manufacturing and other preparation pro-
cesses [32]. The effect of the solid–liquid ratio on the metal leach-
ing efficiency with 0 rpm stirring speed, 0.6 M HAc, 0.2 M NaCl, at
323.15 K with timeic addition of H2O2 of 12 mL every 2 h is shown
in Fig. 4. Fig. 4(a) shows the LR of Cu with various solid–liquid
ratios from 5 to 25 g/L. In the same leaching time, the LR of Cu
gradually increased as the solid-to-liquid ratio decreased from
25 g/L to 10 g/L. In particular, the highest LR of Cu was obtained
in 10 h, which was 73.19%. However, continuing to reduce the
solid–liquid ratio has a slight improvement in the LR of Cu. Fig. 4
(b) exhibits similar leaching behavior to Fig. 3(b). When the leach-
ing time was 10 h, the LR of Fe increased from 52.44% to 68.06%
with the solid–liquid ratio decreased from 25 g/L to 10 g/L, the
LR of Fe was only 69.98% as the solid–liquid ratio further decreased
to 5 g/L. In summary, considering the leaching efficiency and cost
consumption, the solid–liquid ratio should be adjusted to 10g/L
to ensure the ideal leaching performance of Cu and Fe.
The solid–liquid ratio significantly affects the leaching perfor-
mance of Cu and Fe from chalcopyrite powder. The leaching effi-
ciency of Cu and Fe deteriorated with increasing solid–liquid
ratio. This could be attributed to the following aspects. One possi-
ble explanation is that the number of solids per unit of solvent
increased as the solid–liquid ratio increased, resulting in insuffi-
cient amounts of necessary reagents in the solution. In other
words, the solution environment required by the solid reactant
had not reached the optimal conditions. In addition, some reports
indicated that the rapid decomposition of H2O2 in a more concen-
trated suspension may lead to undesirable overall reaction results
[33]. The viscosity of the suspension increased due to the high solid
3
H. Chen, J. He, L. Zhu et al.
Fig. 3. Effect of stirring speed on leaching of Cu and Fe from chalcopyrite powder.
Fig. 4. Effect of solid–liquid ratio on leaching of Cu and Fe from chalcopyrite powder.
phase, which led to the agglomeration of chalcopyrite powder.
Therefore, the contact between the leaching liquid and the internal
chalcopyrite powder was insufficient, and the efficiency of the
leaching process was poor [34]. The decrease in the solid–liquid
ratio during the leaching process was equivalent to the expansion
of the reaction solution volume. As a result, the chalcopyrite
powder was better immersed in the solution and the solution
was completely contact with chalcopyrite powder at the suitable
solid–liquid ratio, thus improving the mass transfer efficiency
and leaching performance.
3.1.3. Effect of HAc concentration
The effect of acid concentration on metal leaching should be
thoroughly investigated as it directly determined process control
and economics [35]. Fig. 5 illustrates the effect of the HAc concen-
tration on the metal leaching efficiency with 0 rpm stirring speed,
the solid–liquid ratio of 10 g/L,0.2 M NaCl, at 323.15 K with timeic
addition of H2O2 of 12 mL every 2 h. As shown in Fig. 5(a), the con-
centration of HAc has a significant impact on the LR of Cu. With the
extension of the leaching time, the LR of Cu continued to increase
and reached the maximum value in 10 h. When the leaching time
was 10 h, the LR of Cu firstly increased from 62.60% to the peak
value and then gradually decreased to 64.54% as the increase of
HAc from 0.3 M to 0.7 M. Particularly the LR of Cu presented the
maximum value of 78.19% at HAc concentration = 0.5 M. As pre-
sented in Fig. 5(b), the variation trend of LR of Fe with HAc concen-
4
Advanced Powder Technology 33 (2022) 103547
tration is not significantly various from LR of Cu. When the HAc
concentration = 0.3–0.4 M, the LR of Fe increased to 45.18% and
51.55%, respectively, with the leaching time from 2 h to 8 h, and
then slowly increased to 48.05% and 58.90% as the leaching time
further increased to 10 h. When the concentration of HAc was
increased to 0.5 M, the overall LR of Fe was the highest, and the
maximum value of 68.06% was obtained at 10 h. However, with
the further increase of HAc concentration, the overall leaching rate
of Fe decreased, and the LR of Fe at 10 h with 0.7 M HAc concentra-
tion was only 59.35%. Therefore, both considering the LR of Cu and
Fe, the optimal HAc concentration should be adjusted around 0.5 M
to ensure notable leaching efficiency.
As is known to all, HAc has special volatility and weak acidity
[22], long-term exposure to the air causes the concentration of
HAc in the solution to decrease continuously. This explains that
the relationship between the metal leaching rate and the leaching
time under the condition of a low concentration of HAc is not a
beeline. Besides, As shown in Eq. (4), HAc incompletely ionized a
large amount of H+ in the leaching solution.
CH3 COOH þ H2 O¢Hþ þ CH3 COO
ð4Þ
The increase in the pH of the solution led to a significant
increase in the oxidation rate of chalcopyrite [36], which could
be explained as the increase in the redox potential of H2O2 due
to the increase in the concentration of H+.
H. Chen, J. He, L. Zhu et al. Advanced Powder Technology 33 (2022) 103547

Fig. 5. Effect of HAc concentration on leaching of Cu and Fe from chalcopyrite powder.

It was reported that the decomposition of H2O2 could be mod- slowly increased to 74.96%. Therefore, the concentration of NaCl
estly inhibited by HAc due to the similarity of H2O2 and HAc polar- should be kept at about 0.4 M to optimize the leaching perfor-
ity [37]. As shown in Fig. 6, various decomposition rates of H2O2 mance of chalcopyrite powder.
can be observed obviously when isodoses H2O2 were added in The positive roles of NaCl on the dissolution of chalcopyrite
0.3–0.7 M HAc solutions. The bubbles generated by the solution powder may be due to the complex dependence on Cl
concentra-
gradually decreased as the concentration of HAc increased, which tion [39]. The presence of Cl
in the electrolyte solution can form
indicated that the decomposition of H2O2 was violent at 0.3 M stable complexes (Eqs. (5)–(12)) [32] with metal cations (Cu2+,
HAc, while at a concentration of 0.7 M HAc, there is only a slight Fe3+) may have a considerable impact on the dissolution [40,41]
decomposition. However, the increased stability also hindered of the chalcopyrite powder’s surface. Therefore, the rate of metal
the reaction rates of H2O2 with chalcopyrite powder. This meant oxidation and overall leaching may be increased. In addition, due
that higher temperatures and longer time should be required to to the superior association affinities of Cl
to metal cations, high
obtain the ideal leaching performance. Cu2+ activity and Fe3+ activity can be maintained. It has been
shown that a higher oxidation potential is observed in a proper
3.1.4. Effect of NaCl concentration concentration of NaCl solution, and the current density is higher
Determining the optimal concentration of Cl
ions was signifi- than without this substance [42].
cant for commercial leaching because a large amount of Cl
ions

þ
existed in industrial water [38]. Fig. 7 shows the effect of the NaCl Cu2þ þ Cl
CuCl ð5Þ
concentration on the metal leaching efficiency with 0 rpm stirring


speed, the solid–liquid ratio of 10 g/L, 0.5 M HAc, at 323.15 K for Cu2þ þ 2Cl
CuCl2 ð6Þ
10 h with timeic addition of H2O2 of 12 mL every 2 h. As presented



in Fig. 7(a), the LR of Cu was improved notably by adding NaCl. Cu2þ þ 3Cl
CuCl3 ð7Þ
When the leaching time was 10 h, the LR of Cu was only 65.18%
without NaCl. However, the overall LR of Cu increases rapidly as
2

Cu2þ þ 4Cl
CuCl2 ð8Þ
NaCl was introduced. The maximum LR of Cu was obtained of
78.58–84.98% with 0.2–0.8 M NaCl. In particular, the highest LR

Fe3þ þ Cl ¼ FeCl
2þ
ð9Þ
of Cu presented a slight fluctuation of 83.18–84.98% as the concen-
tration of NaCl increased from 0.4 M to 0.8 M. As illustrated in
þ
Fe3þ þ 2Cl ¼ FeCl2 ð10Þ
Fig. 7(b), similar leaching results were found in the LR of Fe. The
LR of Fe presented an obvious increase as the increase of leaching

Fe3þ þ 3Cl ¼ FeCl3 ð11Þ
time. Besides, the LR of Fe at 10 h was 56.69% without NaCl. With
0.4 M NaCl, the LR of Fe at 10 h increased sharply to 73.36%. How-
þ
Fe3þ þ 4Cl ¼ FeCl4 ð12Þ
ever, with the further increase of NaCl concentration, the LR of Fe

Fig. 6. Leaching phenomena of Chalcopyrite powder when adding 10 mL H2O2 in 4 h.

5
H. Chen, J. He, L. Zhu et al.
Fig. 7. Effect of NaCl concentration on leaching of Cu and Fe from chalcopyrite powder.
Another possible reason for the increased leaching efficiency in
the presence of Cl
is that the Cl
promoted the formation of por-
ous sulfur [43] layers on the chalcopyrite powder surface, favoring
metal extraction. The orthorhombic ring (S8) was the main solid
form and the most stable form of the sulfur allotrope. This phase
was also considered to be the residual chalcopyrite lattice struc-
ture [44].
The morphological structure of the leaching residue with/with-
out NaCl obtained as a result of the leaching test was characterized
by scanning electron microscopy (SEM, FEI Quanta 250, America).
Before characterization, the residue specimens were pretreated
with gold coating. Electron microscope images of the leaching resi-
due obtained under a high vacuum environment are shown in
Fig. 8. HAc caused the formation of layered crystal aggregates of
product sulfur on the surface of chalcopyrite powder under oxidiz-
ing conditions. As presented in Fig. 8(a), the compact surface struc-
ture of the leaching residue and adhesion of the conchoidal sulfur
element are observed. This could be verified by the content of
72.47% S from Fig. 9. It can be seen from Fig. 8(b) that sulfur
appears in the form of a porous, tufted structure as 0.4 M NaCl
added. The surface of the filter residue was loose instead of form-
ing a continuous film. High porosity meant that there was enough
open space between sulfur and unreacted chalcopyrite powder,
which contributed to the diffusion of reagents between the reac-
tion sites. Nicol [45] found that in acid chlorides, the dissolution
of chalcopyrite exhibited a complex dependence on the Cl
con-
Fig. 8. SEM image of chalcopyrite leaching residue after 10 h leaching in the 10 g/L, 0.5 M HAc, with 12 mL H2O2 added every 2 h, at 323.15 K (a): 0 M NaCl; (b): 0.4 M NaCl.
6
Advanced Powder Technology 33 (2022) 103547
centration, and the Cl
could increase the anode current [46]. In
conclusion, Cl
was essential for the dissolution of chalcopyrite
powder.
However, the Cl
concentration has a certain upper limit to the
metal complexing ability as there is a complex equilibrium con-
stant between the metal ions and the Cl
[47]. Therefore, the leach-
ing of metals from chalcopyrite powder can be slightly improved in
an excessively high concentration of Cl
solution.
3.1.5. Effect of H2O2 volume
In the acidic oxidation leaching process of chalcopyrite powder,
H2O2 plays a significant oxidant in the reaction system [48]. Fig. 10
shows the variation regulation of the LR of Cu and Fe from chal-
copyrite powder when 4–20 mL H2O2 (30%, AR) is added every
2 h with 0 rpm stirring speed, the solid–liquid ratio of 10 g/L,
0.5 M HAc, 0.4 M NaCl, at 323.15 K. As illustrated in Fig. 10(a),
the LR of Cu is significantly affected by the leaching time and vol-
ume of H2O2. When the added H2O2 volume was in the range of 4–
16 mL, the LR of Cu increased with the extension of the leaching
time, and reached the maximum value at 10 h. In addition, the
maximum LR of Cu sharply increased from 52.31% to 96.13% as
the increase of H2O2 volume from 4 mL to 16 mL. However, when
the added H2O2 volume was 20 mL, the LR of Cu reached its peak at
6 h and then increased very slowly as the leaching time extended
to 10 h. As presented in Fig. 10(b), the volume of H2O2 has a similar
effect on the LR of Fe. With the leaching time of 10 h, the LR of Fe
H. Chen, J. He, L. Zhu et al.
Fig. 9. EDS spectrum point analysis from the point indicated in Fig. 8.
Fig. 10. Effect of H2O2 volume on leaching of Cu and Fe from chalcopyrite powder.
increased from 46.42% to 84.35% as the increase of added H2O2 vol-
ume from 4 mL to 16 mL. A further increase in the volume of H2O2
made the LR of Fe reach a peak of 69.85% in 6 h, and the LR of Fe
only slightly increased to 74.12% when extended the leaching time
to 10 h. In summary, the added H2O2 volume should be adjusted to
16 mL every two hours to ensure the ideal leaching performance of
Cu and Fe.
The main substance of H2O2 to oxidize minerals is its decom-
posed hydroxyl radical (OH*) [49] according to Eq. (13):
H2 O2 ! HO þ OH
ð13Þ
It can be concluded that increasing the concentration of H2O2
may produce more HO*s in the mixed solution. Therefore, higher
initial potential and a faster initial leaching rate can be obtained.
According to Blight [50], there exists substantial covalency
between the S anions and metal cations in the CuFeS2 structure.
When electrons in CuFeS2 are extracted by suitable redox-active
species, these chemical bonds may be broken [51]. These broken
chemical bonds can be still present on the CuFeS2 surface leading
to a greater interfacial reactivity and increased dissolution or oxi-
dation rate [52]. However, as the leaching process progresses, Fen-
ton’s reagent is continuously generated in the solution to promote
the decomposition of H2O2 [53]. In addition, because the decompo-
7
Advanced Powder Technology 33 (2022) 103547
sition rate of H2O2 is greater at higher concentrations, as the initial
concentration of H2O2 increases, the actual amount of H2O2 that
reacts with chalcopyrite powder decreases, thus a non-linear devi-
ation of the leaching curve is observed.
It has been reported that with the condition of excessive H2O2, a
passivation film on the surface of chalcopyrite powder is observed,
which hinders the dissolution of chalcopyrite [54]. The morphol-
ogy investigation of leached chalcopyrite sample is performed
using SEM, which is shown in Fig. 11. The surface of unreacted
chalcopyrite powder was no longer observed. They are mostly sur-
rounded by porous agglomerates of elemental sulfur, which was
previously proven in Fig. 8. In order to further verify the composi-
tion of the passivation film on the surface of chalcopyrite, EDS
spectrum point analysis of selected points from the SEM image is
shown in Fig. 12. The intense peak of sulfur was found in the
EDS analysis result at point 1, and the sulfur content was about
55.72%. It should be mentioned that the non-conductive of solid
unshaped sulfur leads to higher brightness by local electron accu-
mulation. Interestingly, we also found about 2.88% Na in the leach-
ing residue of chalcopyrite powder in point 1. This may be
attributed to the passivation mechanism of Fe3+. It is generally
accepted that Fe3+ can be hydrolyzed under strongly oxidizing con-
ditions (such as acidic heat conditions) to produce iron hydroxide,
H. Chen, J. He, L. Zhu et al.
Fig. 11. SEM image of chalcopyrite leaching residue after 10 h leaching in the 10 g/
L, 0.5 M HAc, 0.4 M NaCl solution, with 20 mL H2O2 added every 2 h, at 323.15 K.
Fig. 12. EDS spectrum point analysis from points indicated in Fig. 11.
8
Advanced Powder Technology 33 (2022) 103547
oxyhydroxides and jarosite [55,56]. Thus the element of Na on the
surface of chalcopyrite powder may be due to the formation of
natrojarosite [57], which is similar to jarosite. Besides, the peak
of Fe and O was found in the EDS analysis result at point 2, and
the content of Fe and O were 13.21% and 65.53%, respectively. This
may prove that iron hydroxide or oxyhydroxides formed on the
surface of chalcopyrite powder. In summary, chalcopyrite had a
complicated passivation mechanism in the HAc- H2O2-NaCl sys-
tem. The strengthening of Cl
during the leaching process cannot
completely overcome the obstacles of passivation to the leaching
process.
3.1.6. Effect of leaching temperature
The leaching of chalcopyrite is a typical chemical reaction
whose leaching rate is mainly controlled by temperature [58].
Fig. 13 shows the effect of the leaching temperature on the metal
leaching efficiency with 0 rpm stirring speed, the solid–liquid ratio
of 10 g/L, 0.5 M HAc, 0.4 M NaCl, and timeic addition of H2O2 of
16 mL every 2 h. As presented in Fig. 13(a), the LR of Cu could be
significantly improved as the increase of leaching temperature
from 303.15 K to 343.15 K. In particular, the highest LR of Cu of
96.13% was obtained at the leaching temperature of 333.15 K
and the leaching time of 10 h. Although the LR of Cu at 343.15 K
H. Chen, J. He, L. Zhu et al. Advanced Powder Technology 33 (2022) 103547

Fig. 13. Effect of leaching temperature on leaching of Cu and Fe from chalcopyrite powder.

was higher than that of Cu at 333.15 K within 2–8 h, a higher LR
will not be obtained as the leaching time was further extended.
As illustrated in Fig. 13(b), the leaching behavior of Fe was similar
to Cu as the leaching temperature increased. The LR of Fe presented
a notable increase as the increase of leaching time. When the
leaching time was 10 h, the LR of Fe firstly increased from
54.56% to the peak value and then gradually decreased to 81.90%
as the increase of leaching temperature. Particularly the LR of Fe
presented the maximum value of 84.35% at 333.15 K. Therefore,
the leaching temperature should be adjusted at 333.15 K to achieve
the optimum leaching process.
As the leaching temperature increased, the internal diffusion of
the reactants and the external diffusion of the product were
increased, thus enhanced the mass transfer efficiency and the reac-
tion rate of chalcopyrite powder with the leaching solution. As a
result, the overall leaching performance of chalcopyrite powder
improved with the increase of leaching temperature was plausible.
Zhao [59] believed that due to the n-type semiconducting of the
chalcopyrite mine, the transportation of electrons through vacancy
was minimal. The first phase of the oxidation of bras chalcopyrite
mine consumed holes [60], which facilitated the transmission of
electrons through the lattice. Therefore, the heat consumed in
the displacement of the ion from the body to the surface was elim-
inated and the transmission of electrons was promoted [61].
Therefore, moderately high temperatures led to higher currents
and potentials, which was also one of the reasons for the leaching
of metal efficiency from chalcopyrite powder. However, due to the
presence of the Fenton reagent [30] and the fragile thermal stabil-
ity [62] of H2O2, the excessively high temperature did not improve
the leaching efficiency.
3.2. Statistical analysis
Analysis of variance (ANOVA) is a method to analyze experi-
ment data and judge whether each factor has a significant influ-
ence on experiment results [63]. In general, homogeneity test of
variance is required before ANOVA. Most optimal leaching results
were obtained at the leaching time of 10 h. Therefore, the leaching
results from Figs. 3, 4, 5, 7, 10, 13 at 10 h were used to test the
homogeneity of variance. Analysis was performed using SPSS sta-
tistical software, version 18.0. Leven’s test for homogeneity of vari-
ance was performed to assess the homogeneity of variance. The

Table 2
Homogeneity of variance test.

Factors Levene statistic df1 df2 P value

Cu Fe Cu Fe
Stirring speed Based on mean 1.367 3.164 4 10 0.077 0.064
Solid-liquid ratio Based on mean 1.844 0.99 4 10 0.065 0.071
HAc concentration Based on mean 0.971 0.976 4 10 0.197 0.462
NaCl concentration Based on mean 0.866 1.607 4 10 0.517 0.247
H2O2 volume Based on mean 0.208 0.239 4 10 0.928 0.910
Leaching temperature Based on mean 0.489 0.431 4 10 0.744 0.783

Table 3
One-way analysis of variance.

Factors Sum of squares df Mean square F value P value

Cu Fe Cu Fe Cu Fe Cu Fe
Stirring speed 598.526 342.723 4 149.632 85.681 430.5 831.7 <0.001 <0.001
Solid-liquid ratio 1007.417 599.75 4 251.854 149.937 1793.8 3838.5 <0.001 <0.001
HAc concentration 847.95 1025.34 4 211.988 256.335 4679.2 17595.4 <0.001 <0.001
NaCl concentration 784.152 687.878 4 196.038 171.97 6671.5 3245.5 <0.001 <0.001
H2O2 volume 3735.936 2569.49 4 933.984 642.373 29592.9 9931.3 <0.001 <0.001
Leaching temperature 1785.13 1856.11 4 446.283 464.027 3930.8 8348.7 <0.001 <0.001

9
H. Chen, J. He, L. Zhu et al. Advanced Powder Technology 33 (2022) 103547

Fig. 14. Fitting results using various kinetic models of leaching Cu and Fe (a): chemical reaction in SCM for Cu leaching; (b) chemical reaction in SCM for Fe leaching; (c)
diffusion reaction in SCM for Cu leaching; (d) diffusion reaction in SCM for Fe leaching; (e) Avrami equation for Cu leaching (f) Avrami equation for Fe leaching.

results are shown in Table 2. Obviously, the P values >0.05 of all
factors indicated that the leaching results can be used for ANOVA.
As one of the most common methods of ANOVA, one-way
ANOVA can be used to test differences between groups with more
than three levels [64]. Statistical analysis of results that had been
examined was performed using one-way ANOVA. Table 3 shows
the significance at different levels of each factor between groups.
The F value of Cu and Fe leaching results were the largest when
the factor was H2O2 volume, which were 29592.9, 9931.3, respec-
tively. The larger F value indicates that the variance between
groups is the main source of variance and more significant effect
of different levels treatment on the leaching effect. This conclusion
corresponded to the previous sections. Besides, all the P val-
10
ues < 0.001 also indicated the significant effect of different factors
on the Cu and Fe leaching results.
3.3. Leaching kinetics
In the basic research of leaching, as well as the design of the
plant, the dynamic model is a very effective tool [65]. It has been
proved that the shrinking core model (SCM) [66] assuming isother-
mal nth-order irreversible kinetics can be applied to the chalcopy-
rite ores leaching system [67]. However, due to the complexity of
the leaching medium, it is still controversial whether the chalcopy-
rite leaching process is controlled by chemical reaction (Eq. (14)) or
diffusion reaction (Eq. (15)). Another kinetic equation that is
H. Chen, J. He, L. Zhu et al. Advanced Powder Technology 33 (2022) 103547

employed to describe the metal leaching for some solid–liquid
heterogeneous processes is the Avrami equation (Eq. (16)) [68],
which is a mixed control model, containing diffusion and surface
chemical reaction control. Its natural logarithm form can be
expressed as Eq. (17). Some reports indicated that the Avrami
equation has goodness on the fitting of multi-metal leaching.
Therefore, these models were investigated to verify their suitability
for the leaching data at various temperatures.
1 To determine the effect of reaction parameters on the apparent
1
ð1
xÞ3 ¼ k  t
2
1
3ð1
xÞ3 þ 2ð1
xÞ ¼ k  t

lnð1
xÞ ¼ k  t n
lnð
lnð1
xÞÞ ¼ lnk þ nlnt
where x is the leaching rate, %; k is the apparent rate constant; t is
the leaching time; and n is the parameter that reflected the leaching
process, which is related to the geometry of solid powder.
Based on the data in Fig. 13, the fitting results of the various
equations for the leaching of Cu and Fe from chalcopyrite powder
are shown in Fig. 14. The goodness of fit was verified that the fit-
ting curves of the three kinetic models basically conform to the lin-
ear law. Tables 4 and 5 show the specific kinetic parameters of the
SCM and Avrami equation, respectively. For Cu leaching from chal-
copyrite powder, the diffusion control in SCM seemed to be more
suitable for describing its dynamic behavior with the optimal cor-
relation coefficient (R2) range of 0.9914–0.9996. T-test and F-test
[69] were used for the test of significance of the regression param-
eters and regression equations, respectively (P value < 0.05 was
considered significant). Obviously, all P values < 0.05 indicated that
the regression equation was very significant when the diffusion
control in SCM was used for Cu leaching from chalcopyrite powder,
while part of P values > 0.05 in other models. The optimal R2 range
of 0.9914–0.9977 was obtained when the Avrami equation was
used to fit the kinetic goodness of Fe leaching from chalcopyrite
powder. Similarly, the goodness of Avrami equation was further
proved by P values < 0.05, indicated that the regression equation
was very significant when the Avrami equation was used for Fe
leaching from chalcopyrite powder, while part of P values > 0.05
in other models. In addition, for 0.5  n < 1, the leaching process
is a mixed type of chemical reaction and diffusion control; for
n < 0.5, it is controlled by diffusion reaction [70]. Obviously, the
range of n = 0.1288–0.1999 indicated that the leaching of Fe from
chalcopyrite powder was mainly controlled by diffusion reaction.
ð14Þ rate constant, the mathematical model can be purposed by Eq.
(18):
ð15Þ
k ¼ k0  ðS=LÞa  ðC HAc Þb  ðC NaCl Þc  ðV H2 O2 Þd  expð
Ea =GTÞ ð18Þ
ð16Þ where S/L, CHAc, CNaCl, VH2O2, Ea, G, and T symbolize the stirring speed,
solid–liquid ratio, HAc concentration, NaCl concentration, H2O2 vol-
ð17Þ ume, apparent activation energy, molar gas constant, and thermo-
dynamic temperature, respectively. The constants a, b, c, and d
represent the dependence of the reaction rate to the relevant
parameters, and ko is the frequency factor. Combining Eqs. (15)–
(16), the following equation can be written as:
2
1
3ð1
xÞ3 þ 2ð1
xÞ ¼ k0  ðS=LÞa  ðC HAc Þb  ðC NaCl Þc
 ðV H2 O2 Þd  expð
Ea =GTÞ  t ð19Þ

lnð1
xÞ ¼ k0  ðS=LÞa  ðC HAc Þb  ðC NaCl Þc  ðV H2 O2 Þd
 expð
Ea =GTÞ  t n ð20Þ
The comparison of reaction orders and constant values of reac-
tion parameters can be obtained by Figs. 15,16. Obviously, the vol-
ume of H2O2 had the highest influence on the leaching of Cu and Fe
from chalcopyrite powder. In contrast, the concentration of NaCl
had the lowest effect on the leaching of Cu from chalcopyrite pow-
der, and the solid–liquid ratio had the lowest effect on the leaching
of Fe, respectively. In addition, the constants a, b, c, and d of Cu
leaching using Eq. (15) were found to be
0.46, 0.79, 0.31, and
0.99, respectively. Similarly, the constants a, b, c, and d of Fe leach-
ing using Eq. (16) were found to be
0.26, 0.51, 0.33, and 0.72,

Table 4
Kinetic parameters and regression parameters during the leaching process of Cu and Fe using SCM.

Kinetic Model Temperature (K) Cu Fe

2
R kd P value (T-statistic) P value R2 kd P value P value
(F-statistic) (T-statistic) (F-statistic)
Chemical 303.15 0.9988 0.0471 0.0318 0.0357 0.9926 0.0426 0.0832 0.0504
control 313.15 0.9721 0.0551 0.0814 0.0797 0.9883 0.0509 0.0783 0.0459
323.15 0.9598 0.0659 0.0613 0.0618 0.9707 0.0661 0.0638 0.0944
333.15 0.9901 0.0843 0.0827 0.0759 0.9812 0.0727 0.0185 0.0912
343.15 0.9882 0.0864 0.0109 0.0634 0.9809 0.0712 0.0421 0.078
Diffusion 303.15 0.9914 0.0183 0.0255 0.0312 0.9932 0.0145 0.0625 0.0813
control 313.15 0.996 0.0268 0.0472 0.0147 0.9861 0.0224 0.0753 0.0116
323.15 0.999 0.041 0.0417 0.0116 0.9799 0.033 0.0638 0.0759
333.15 0.9979 0.0595 0.0297 0.0052 0.9926 0.0436 0.0443 0.0921
343.15 0.9996 0.0756 0.0201 0.0201 0.9820 0.0469 0.0192 0.0797

Table 5
Kinetic parameters and regression parameters during the leaching process of Cu and Fe using Avrami equation.

Temperature (K) Cu Fe
R2 lnk P value n P value P value R2 lnk P value n P value P value
(T-statistic) (T-statistic) (F-statistic) (T-statistic) (T-statistic)
(F-statistic)
303.15 0.9833
1.6167 0.0318 0.1492 0.0119 0.0235 0.9972
1.9731 0.0177 0.1288 0.0283 0.0379
313.15 0.9754
1.2155 0.1013 0.1542 0.0185 0.0482 0.9977
1.581 0.0109 0.1473 0.0217 0.0133
323.15 0.9869
0.8774 0.0929 0.1586 0.0483 0.0376 0.9914
1.3583 0.0239 0.1612 0.0221 0.0071
333.15 0.9866
0.9503 0.0362 0.2044 0.0401 0.0148 0.9977
1.1261 0.0162 0.183 0.0104 0.0246
343.15 0.9929
1.0795 0.1587 0.2406 0.0309 0.0862 0.9925
0.9716 0.0233 0.1999 0.0160 0.0172

11
H. Chen, J. He, L. Zhu et al. Advanced Powder Technology 33 (2022) 103547

Fig. 15. The linear relationship between 3(1
x)2/3 + 2(x
1) and reaction orders of various parameters for leaching Cu from chalcopyrite powder (a): S/L ratio (b): reaction
order of S/L ratio; (c): HAc concentration; (d) reaction order of HAc concentration; (e): NaCl concentration; (f): reaction order of NaCl concentration (g): Volume of H2O2 added
every two hours; (h): reaction order of volume of H2O2 added every two hours.

12
H. Chen, J. He, L. Zhu et al. Advanced Powder Technology 33 (2022) 103547

Fig. 16. The linear relationship between ln(-ln(1-x)) and reaction orders of various parameters for leaching Fe from chalcopyrite powder (a): S/L ratio (b): reaction order of S/L
ratio; (c): HAc concentration; (d) reaction order of HAc concentration; (e): NaCl concentration; (f): reaction order of NaCl concentration (g): Volume of H2O2 added every two
hours; (h): reaction order of volume of H2O2 added every two hours.

13
H. Chen, J. He, L. Zhu et al. Advanced Powder Technology 33 (2022) 103547

Table 6
Regression analysis of reaction orders.

Cu Fe
Reaction P value (T-statistic) P value (F-statistic) Reaction P value P value
orders orders (T-statistic) (F-statistic)
a = -0.46 0.0134 0.0307 a = -0.26 0.0148 0.0279
b = 0.79 0.0022 0.0082 b = 0.51 0.0017 0.0033
c = 0.33 0.0159 0.0381 c = 0.33 0.0157 0.0171
d = 0.99 0.0319 0.0288 d = 0.72 0.0204 0.0146

Fig. 17. Arrhenius plots for the leaching of (a) Cu and (b) Fe.

Table 7
Regression analysis of Arrhenius plots and mathematical expressions in chalcopyrite leaching.

Cu Fe
Parameters P value P value Parameters P value P value
(T-statistic) (F-statistic) (T-statistic) (F-statistic)
Ea = 29.11 0.0105 0.0307 Ea = 20.90 0.0117 0.0279
k0 = 0.41 0.0416 0.0322 k0 = 1.87 0.0465 0.0362

Fig. 18. Relationship between (a) Cu and (b) Fe leaching kinetics versus various reaction parameters.

respectively. The leaching reaction was found to be approxi-
mately first order with respect to all reaction parameters except
stirring speed. It is worth specifying that the SCM assumes uni-
form original ore particle size [71]. However, as can be observed
in Fig. 1, the size distribution of the original sample was uneven,
which meant some sample particles with smaller sizes were
expected to be leached out more quickly than others [12]. This
could explain why these lines in Fig. 15 did not pass through
the origin.
Table 6 shows the regression analysis results of reaction orders.
Combined with Fig. 15, for the reaction order regression equation
of Cu, the R2 range of 0.9905–0.999 indicated that the regression
equation had goodness of fit, and all the P values < 0.05 ensured
the significance of the regression equation. Similarly, all the P

14
H. Chen, J. He, L. Zhu et al.
values < 0.05 of Fe reaction order regression equation indicated the
significance of the regression equation, and the satisfactory good-
ness of fit was obtained by the R2 range of 0.9922–0.9955 from
Fig. 16.
In order to further calculate the Ea of the reaction system, the
Arrhenius equations (Eq. (21)) [72] were obtained by using the k/
lnk of the selected model, which are shown in Fig. 17.
Ea 1
lnk ¼
ð Þ þ lnA
G T
where Ea is the apparent activation energy, kJ/mol; G is the molar
gas constant, 8.314 J/(molK); T is the thermodynamic temperature,
K; A is the independent constant.
As shown in Fig. 17, the Ea of Cu and Fe leaching from chalcopy-
rite powder are 29.11 kJ/mol and 20.90 kJ/mol, respectively. Ea
were both smaller than 30 kJ/mol [73], which indicated that the
Cu and Fe leaching from chalcopyrite powder reaction mainly
depended on the controlling of diffusion. Besides, all the P val-
ues < 0.05 indicated the significance of regression equation in
Table 7. It is worth pointing out that the Ea of Fe was smaller than
the Ea of Cu, implying that the leaching of Fe was easier than Cu.
However, the passivation mechanism of Fe inhibits its maximum
leaching rate, causing the optimum leaching performance of Fe
to lower than the leaching rate of Cu, which was consistent with
the results observed in Figs. 11-12.
The ko of kinetic models of Cu and Fe can be estimated by the
slopes from Fig. 18, which are 4.1  10-4 and 1.87  10-3, respec-
tively. The R2 of 0.9639 and 0.9514 indicated that the agreement
between theoretical and experimental values is very good. Besides,
the significance of the regression equations was verified by all the
P values < 0.05. Consequently, a mathematical expression includ-
ing the experimental parameters to represent the leaching kinetics
of Cu and Fe leaching from chalcopyrite powder in HAc-H2O2-NaCl
system may be written as follows:
2 [3] C. Klauber, A critical review of the surface chemistry of acidic ferric sulphate
1
3ð1
xÞ3 þ 2ð1
xÞ ¼ 4:1  10
4  ðS=LÞ
0:46  ðC HAc Þ0:79
 ðC NaCl Þ0:31  ðV H2 O2 Þ0:99
 expð3501:74=TÞ  t

lnð1
xÞ ¼ 1:87  10 -3
 ðS=LÞ
0:26  ðC HAc Þ0:51  ðC NaCl Þ0:33
 ðV H2 O2 Þ0:72  expð2514:25=TÞ  t 0:16
4. Conclusion
(1) As an eco-friendly organic acid, HAc can achieve efficient
leaching of Cu and Fe from chalcopyrite powder with NaCl
and H2O2. Under the optimal leaching conditions of no stir-
ring speed, solid–liquid ratio of 10 g/L, 0.5 M HAc, 0.4 M
NaCl, at 333.15 K for 10 h with timeic addition of H2O2 of
16 mL every 2 h, the leaching rate of 96.13% Cu and
84.35% Fe were obtained.
(2) The kinetics of the leaching of Cu appeared to follow the
shrinking core model while the leaching of Fe appeared to
follow the Avrami equation. Besides, all the leaching pro-
cesses mainly depended on the controlling of diffusion
through evaluating the apparent activation energies of Cu
and Fe, which were 29.11 and 20.90 kJ/mol, respectively.
(3) The leaching of Cu and Fe from chalcopyrite powder was
found to be approximately first order with respect to all
reaction parameters except stirring speed. The volume of
H2O2 had the greatest effect on the leaching rates, the reac-
tion order with respect to H2O2 volume over Cu and Fe
leaching were 0.99 and 0.72, respectively.
Advanced Powder Technology 33 (2022) 103547
(4) The SEM-EDS analysis of the leaching residue of chalcopyrite
powder showed that the porous elemental sulfur was the
main by-product of the leaching of chalcopyrite. Iron
hydroxide, oxyhydroxides and natrojarosite by passivation
limited the maximum leaching rate of Fe, causing the leach-
ing efficiency of iron from chalcopyrite powder to be lower
than that of Cu.
ð21Þ
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
This work was supported by The National Natural Science Foun-
dation of China (No. 52074289); The Science and Technology Pro-
ject of Xuzhou city, China (No. KC20173); The Open Foundation of
State Key Laboratory of Mineral Processing (No. BGRIMM-KJSKL-
2020-18); The Sponsored Project of Jiangsu Provincial Six Talent
Peaks, China (No. JNHB-080); and The Financial Support Project
of National & Local Joint Engineering Research Center for Deep
Utilization of Mineral-salt Resources (No. SF201701).
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