Colloids and Surfaces A: Physicochemical and Engineering Aspects 644 (2022) 128799

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Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Understanding the effect of grinding media on the adsorption mechanism of

cyanide to chalcopyrite surface by ToF–SIMS, XPS, contact angle, zeta
potential and flotation
Qianfei Zhao a, b, Hongying Yang a, b, *, Linlin Tong a, b, *, Ruipeng Jin a, b, Pengcheng Ma c
a
Key Laboratory for Ecological Metallurgy of Multimetallic Mineral (Ministry of Education), Northeastern University, Shenyang 110819, Liaoning, China
b
School of Metallurgy, Northeastern University, Shenyang 110819, China
c
Technology Center, Shandong Zhaojin Group Co., Ltd., No. 108 Shengtai Road, Zhaoyuan 265400, China

G R A P H I C A L A B S T R A C T

A R T I C L E I N F O A B S T R A C T

Keywords: As the main copper-bearing sulfide minerals in cyanide tailings, how to improve the flotation recovery of
Ceramic media chalcopyrite is of great significance to the comprehensive management of bulk solid waste. To obtain higher
Iron media leaching rate of precious metals, fine grinding is required. However, the production of numerous interfering ions,
Cyanide leaching
accompanied by severe mechanical entrainment, leads to a series of problems in the grinding process. In this
Chalcopyrite
ToF–SIMS
context, the correlation between surface adsorption, the occurrence of species on the chalcopyrite surface and the
Flotation differences in grinding media in cyanidation system would be a key issue for process optimization. Scanning
electron microscope–energy dispersive spectrometer (SEM–EDS) and contact angle measurements were per­
formed on the chalcopyrite surface. The results showed that the use of ceramic media avoided excessive surface
oxidation caused by the galvanic couple actions between the iron media and chalcopyrite. Zeta potential values
revealed that the cyanide adsorbed on the chalcopyrite surface and reacted with positively charged substances,
inhibiting the adsorption of collector, which was confirmed by microflotation. Surface chemistry analysis using
X–ray photoelectron spectroscopy (XPS) and time–of–flight secondary ion mass spectrometry (ToF–SIMS)
confirmed that the chemical environment of the chalcopyrite surface had been changed using the iron media,
which accelerated the formation of FeOOH and enhanced the adsorption of CN– on the chalcopyrite surface. It
was further demonstrated by ToF-SIMS that the ceramic media exhibited the excellent grinding performance,
which excluded the insignificant contribution of impurity elements (mainly Fe). This study provides important
surface chemical evidence to gain an in-depth understanding of the effect of grinding environment on the

* Corresponding authors at: Key Laboratory for Ecological Metallurgy of Multimetallic Mineral (Ministry of Education), Northeastern University, Shenyang
110819, Liaoning, China.
E-mail addresses: [email protected] (Q. Zhao), [email protected] (H. Yang), [email protected] (L. Tong), [email protected]
(R. Jin), [email protected] (P. Ma).

https://doi.org/10.1016/j.colsurfa.2022.128799
Received 5 January 2022; Received in revised form 9 March 2022; Accepted 15 March 2022
Available online 17 March 2022
0927-7757/© 2022 Elsevier B.V. All rights reserved.
Q. Zhao et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 644 (2022) 128799

mechanism of cyanide adsorption on the chalcopyrite surface, which plays a crucial role in promoting the
possibility of the comprehensive utilization of the cyanide tailings.

1. Introduction generated by the dissolution of chalcopyrite activates the pyrite, which

affects the flotation separation of chalcopyrite and pyrite. In addition,
Cyanide tailing is highly toxic, persistent, concealed and refractory researcher studied the flotation performance of a complex lead-zinc ore
due to the present of cyanide, thiocyanate, heavy metals and other by changing the grinding environment. However, there is still research
pollutants [1,2]. Landfilling or stacking cyanide tailings not only oc­ gap on the role of grinding in the cyanide leaching process, especially
cupies a lot of land, but also causes huge environmental pollution. At the whether grinding media has a greatly impact on the interface properties
same time, cyanide tailings contain a large number of valuable metal of chalcopyrite and the formation of contaminants.
elements, such as gold, silver, copper, lead and zinc. Especially, copper Consequently, understanding the effect of grinding media on the
mainly exists in the forms of chalcopyrite in cyanide tailings [3–5]. As a mechanism of cyanide adsorption on chalcopyrite surface from the
secondary resource, the recovery of valuable elements from cyanide perspective of surface chemistry is the key to clarifying important ar­
tailings have received widespread attention. For chalcopyrite, flotation guments. In this study, SEM-EDS and contact angle were used to describe
is the main means to recovery it from cyanide tailings. Thus, historically, the changes in chalcopyrite surface morphology and wettability,
the process of chalcopyrite flotation in cyanide tailings and its control combining with microflotation and zeta potential, the difference in
strategies have gained extensive attention. grinding media was correlated with cyanide adsorption on chalcopyrite
Ai et al. [6] found that the NaCN had a strong inhibitory effect on surface and its flotation reaction. The surface contaminant compositions
chalcopyrite surface, and the maximum flotation recovery of chalco­ of chalcopyrite were investigated by XPS and ToF-SIMS. The differences
pyrite was only 22.50% with a BX dosage of 0.1 mol/m3. Various studies in the influence on cyanide adsorption between ceramic media and iron
emphasized that cyanide leaching changed the interfacial properties of media were further compared by normalization peak intensity. The
the chalcopyrite surface, inhibiting the adsorption of collector and purpose of this study is to further deepen the theoretical understanding
reducing flotation recovery [7–12]. Nonetheless, the mechanism by of the influence of grinding environment on cyanide adsorption and
which cyanide inhibits the chalcopyrite flotation remains controversial. flotation of chalcopyrite, and to provide a practical reference for the
Some research have reported that the chalcopyrite particles in the cya­ recovery and utilization of copper in cyanide tailings.
nide tailings were fine and porous. In the process of flotation, 68% of
chalcopyrite was similar to galena flotation in the presence of collector, 2. Experimental
which was not conducive to the separation of copper and lead [13].
Other researchers observed that although BX improved the hydropho­ 2.1. Materials and reagents
bicity of the chalcopyrite surface during flotation, the presence of CN−
significantly reduced the chalcopyrite surface’s contact angle (decreased Chalcopyrite sample used in this work was obtained from Guangxi
from 59.8◦ to 35◦ ) [14]. The chemical absorption of X− on the chalco­ Province, China. The mineral blocks were manually selected, washed
pyrite surface is weaker than CN− below pH 8.9. Yang et al. [15] pre­ and dried, the sample was crushed to − 1 + 0.5 mm particle size by using
dicted the main chalcopyrite species in the chalcopyrite–xanthate (X)– a pulverizer (SJ1000–1, Jiangxi, China). The processed samples were
H2O system and the chalcopyrite–NaCN–H2O system by simulating cy­ saved in a vacuum drier used for mill feed. Table 1 and Fig. 1 show the
anide leaching conditions and using the Eh-pH diagrams. The results chemical element composition (ICP–OES, Avio500) and XRD patterns
showed that in the absence of sodium cyanide, with copper ions as active (D8 Advance, Brooke, Germany) of chalcopyrite sample, respectively.
sites, the stable field of the hydrophobic cuprous xanthate dominated in The diffraction peaks in the XRD image correspond to the chalcopyrite
the acidic–alkaline region. However, in the presence of sodium cyanide,
the generation potentials of Fe(CN)64− and Cu(CN)43− are lower than
that of CuX. Therefore, these are the main depressing components that
influence chalcopyrite flotation. In addition, Zhao et al. [16] claimed
that the main contaminants on the chalcopyrite surface were CN− ,
CNO− , CNS− and copper-containing cyanide complexes through
ToF–SIMS measurement, excluding the exist of Fe(CN)64− .
In order to improve the leaching rate of gold, the ball milling with
iron medium is used to regrind the gold concentrate to improve the
fineness of the gold concentrate. In the process of regrinding, Fe element
of is transferred into the cyanide gold extraction system, which not only
increases the impurity content of the system, but also increases the
consumption of cyanide, resulting in the comprehensive recovery of
cyanide tailings more difficult. Peng et al. [17–19] found that moderate
oxidation and changing the grinding media were beneficial to the sep­
aration of sulfide ore. The optimal results for the flotation separation of
galena from pyrite can be obtained by selecting the grinding environ­
ment and thus controlling the oxidation products of lead and iron. A
metal-deficient sulfur-rich surface formed by the oxidized chalcopyrite
surface that facilitates the flotation of chalcopyrite. The copper ions Fig. 1. X-ray diffraction pattern of chalcopyrite sample (− 75 µm).

Table 1
Chemical compositions of chalcopyrite sample (wt%).
Component Cu Fe S SiO2 HfO2 Al2O3 As2O3 CaO ZrO2 Others

Content 33.30 30.50 34.40 0.49 0.20 0.10 0.05 0.02 0.02 0.92

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Q. Zhao et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 644 (2022) 128799

Fig. 2. SEM (at different magnifications), EDS and contact angle images of chalcopyrite samples obtained using different grinding media at a rotating speed of 400 r/
min for 10 min: (A) and (a) ceramic media; (B) and (b) iron media.

crystal phase, which meet the experimental requirements. Zirconium 100 mL flotation tank, mixed with an appropriate amount of high pure
balls (Ceramic Media–CM) and cast iron balls (Iron Media–IM) were water, and stirred for 1 min at an impeller speed of 1500 r/min. NaOH
purchased from Miqi Instrument Equipment Co., Ltd., Hunan Province, and HCl were used to adjust the pH of slurry to 9–10. Sodium butyl
China. xanthate (SBX) and terpenic oil (20 g/t) were added in turn, stirring for
High purity water (Milli-Q integral-5, 18.2 MΩcm) was used for all 3 min and 1 min, respectively. The scraped froth was manually collected
the experiments. Sodium cyanide (NaCN), collector (Sodium butyl for 5 min, the flotation recovery of chalcopyrite samples was calculated
xanthate, SBX) and frother (terpenic oil) of chalcopyrite were provided based on the mass of froth and tailings. The flotation test was repeated
by Shandong Zhaojin Group co., Ltd. All the reagents used in this work three times under the same conditions and the mean value was taken as
were analytical reagent (AR). the final result.

2.2. Chalcopyrite grinding and cyaniding 2.4. Analytical methods

10 g chalcopyrite samples combined with 7 mL high pure water were 2.4.1. Determination of cyanide concentrations
ground using 100 g of zirconium balls or cast iron balls as grinding The concentration of free cyanide in cyanide slurry was determined
medium. The grinding process was carried out in planetary ball mill by silver nitrate titration method. Thymol phthalein and P-dimethyla­
(QM3SP2) instrument equipped with 100 mL zirconium jars. The sam­ minobenzylidene rhodanine were used as indicators. A certain amount
ples were ground at a rotating speed of 400 r/min for 10 min (100% of of cyanide slurry solution was centrifuged and separated. 1 mL of su­
the ground chalcopyrite less than 45 µm in diameter). After grinding, the pernatant was added to a triangular flask, and adjusted pH to 12 using
slurry was transferred to a 600 mL glass beaker containing 400 mL 0.1% 1 M NaOH solution, then added 3–5 drops of indicators and titrated the
NaCN. 1 M NaOH was used to adjust the slurry pH in the range of free cyanide with silver nitrate until the solution changed from black-
11.0–11.5. The cyanide leaching tests were carried out in a mixer (XITII, green to purplish red. Three parallel samples were conducted and the
Jilin, China) at stirring speed of 900 r/min. Throughout the cyanidation mean value was taken as the final result.
process, timely replenish the consumed cyanide to ensure that the NaCN
concentration was kept at 0.1%. Three parallel samples were set up for 2.4.2. Zeta potential analysis
each group. The zeta potential analysis was conducted using a Malvern Zetasizer
Nano ZS90 instrument (Malvern Inc., UK). After adding 50 mg samples
2.3. Microflotation tests (–5 µm) to a beaker and mixing with 50 mL of high pure water, the
desired pH values was adjusted by NaOH or HCl. The mixture was stirred
The flotation tests were carried out in a XFG flotation machine by a magnetic stirrer (T09–1S, Sile, China) for 15 min to thoroughly
(Changchun, Jilin Province, China). In each flotation test, 5 g chalco­ disperse the chalcopyrite. After standing for 10 min, the supernatant
pyrite sample obtained by grinding and cyanidation were added to a was collected and used for zeta potential measurements. All zeta

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Q. Zhao et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 644 (2022) 128799

Fig. 3. Effect of SBX concentration on recovery and grade of chalcopyrite and Cu as a function of grinding media in the presence of 20 g/t terpenic oil.

potentials were measured in quintuplicate and the average was used as amount of oxygen-containing flocculent substances had been formed
the final value. and scattered on the chalcopyrite surface, which was clarified by the
EDS analysis (Fig. 2(a) and (b)). It is worth noting that both the local cell
2.4.3. Morphology analysis actions and galvanic couple actions (caused by the difference of elec­
To understand the wettability of chalcopyrite surface obtained under trostatic potential between the media and the mineral) existed in the
different conditions, the free sessile drop method with a contact angle iron media system. As the electrostatic potential of iron ball
device (DSA25, Kruss, Germany) was used to measure the contact angle (E = − 0.255 V) is smaller than that of chalcopyrite (E = 0.355 V), the
of the chalcopyrite samples. The sample was pressed into a smooth slice anodic oxidation and cathodic reduction reactions occurred on the
with a diameter of 1 cm. A high purity water drop was placed on the chalcopyrite surface [20–22]. The main reactions are shown in Eqs. (1)–
slice surface and the profile of the drop was recorded by digital (6) [21,23,24].
photography at 0.4 s intervals. The average value was obtained from Anodic reaction:
three different locations measured for each sample. The morphology,
Fe⇄Fe2+ + 2e (1)
composition and existing state of the samples were analyzed by a
scanning electron microscope equipped with energy dispersive spec­
CuFeS2 ⇄CuS + Fe2+ S0 + 2e (2)
trometer (SEM–EDS, Quanta250FEG, Germany). The element composi­
tion is the average of five EDS test results in SEM images.
1/2O2 + 2Fe2+ ⇄2Fe3+ O2- (3)
2.4.4. XPS analysis
Fe3+ + 3H2 O⇄Fe(OH)3 + 3H2+ (4)
XPS analysis (250Xi–type, Thermo Fisher Scientific, America) was
used to identify the surface species of chalcopyrite obtained by cyani­
2Fe3+ + O2- + 4OH- →FeOOH + H2 O (5)
dation under different grinding media. The XPS test was performed with
a monochromatic Al Kα X–ray (hv = 1486.6 eV), operated at 30 KeV and Cathodic reaction:
150 W. The C 1s peaks at 284.6 eV was used to calibrate the binding
1/2O2 + 2H2 O + 2e⇄2OH- (6)
energy. Data acquisition and processing were all carried out on the
CasaXPS software. In addition, chalcopyrite particles present a high proportion of
dispersed angular particles due to frequent and strong impact and fric­
2.4.5. ToF–SIMS analysis tion caused by iron balls directly acting on the sample in the process of
Chemical properties on the surface of chalcopyrite obtained by ball milling, while in the case of ceramic media, these particles exist in
cyanidation under different grinding media were performed using trace amounts. According to the contact angle data, the chalcopyrite
ToF–SIMS V (ION–TOF, Münster, Germany). Using a 30 KeV Bi+ as the samples prepared by ceramic medium showed better hydrophobicity
primary ion beam with a current of 0.47 pA, the raster area of the (74.7◦ ) than that of iron medium (59.6◦ ).
samples surface detected for mass spectrometry was 500 µm × 500 µm.
The secondary ions of C+, CH3+ and Fe+ were used as calibration points
in positive mode, and C–, CH– and S– in negative ion mode. 3.2. Effect of grinding media on chalcopyrite floatability in a cyanide
system
3. Results and discussion
The flotation tests of chalcopyrite treated by different grinding
3.1. Effect of grinding media on the surface of chalcopyrite media after cyanide leaching were carried out to verify the floatability of
these grinding products. Fig. 3 shows that with an increase in the SBX
After grinding, a series of characteristics were carried out on the dosage from 0 to 60 mg/L, the flotation recovery increased from 3.73%
ground samples, including surface morphology and wettability, so as to (ceramic media) and 0.87% (iron media) to 19.31% and 13.76%,
explore the influence of grinding media on the surface properties of respectively. Previous researches reported that the cyanide can deeply
chalcopyrite. SEM–EDS and contact angle images of chalcopyrite ground inhibit the flotation of chalcopyrite [14,25,26]. Cyanidation results in
with ceramic media and iron media are shown in Fig. 2 (A and a) and (B hydrophilic products on the minerals surface, such as CN–, CNO–, SCN–
and b), respectively. SEM results show that the samples were composed and CuCN, which increases the interface wettability and is not condu­
of compact particles with severe corrosion and different size. A large cive to the adsorption of collector (Eqs. (7)–(12)) [13,16,27,28]. In this
study, the results of flotation tests indicate that the iron media had a

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Q. Zhao et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 644 (2022) 128799

Table 2
Microflotation results for chalcopyrite samples obtained by cyanidation under different grinding media as a function of SBX in the presence of 20 g/t terpenic oil.
Products Yield (%) Grade (%) Recovery (%)

Cu Fe S Cu Fe S

Ceramic media Concentrate 19.31 33.14 30.01 34.52 19.22 19.00 19.38
Tailings 80.69 33.21 30.95 34.23 80.78 81.00 80.62
Iron media Concentrate 13.76 32.94 31.41 33.98 13.61 14.17 13.59
Tailings 86.24 33.12 30.96 33.79 84.39 85.83 84.41

surface were involved in more reactions [29]. It can be seen that the
grinding media influences the attachment state of the chalcopyrite
surface products, resulting in the CN– selectively reacts with the chal­
copyrite interface products during the cyanidation stage. In addition, the
more negative charges adsorbed on the chalcopyrite surface, trigger to
the disadvantage of collector adsorption.

3.4. Characteristic analysis of cyanide leaching residue

3.4.1. SEM and contact angle analysis

Cyanidation is a complex physicochemical process. The high alka­
line, oxygen-rich environment of cyanidation solution inevitably leads
to a series of problems, such as serious oxidation of the mineral surfaces,
high consumption and low selective adsorption of flotation reagents, the
production of numerous interfering ions. The SEM morphology and
contact angle can directly reflect the interface state and wettability of
samples. As shown in Fig. 5, the surface of the cyanide leaching residue
consisted of dense particles with different sizes and patterns. The cya­
nide chalcopyrite samples obtained from different grinding media
exhibited extremely complex patterns, including circular, prismatic and
irregular shapes. However, the agglomerates phenomenon can be
Fig. 4. Zeta potential of cyanide chalcopyrite as a function of pH under
observed in the iron media samples, and the particle size of the ag­
different grinding media in the presence of 0.1% NaCN.
glomerates is significantly larger than that of finer chalcopyrite obtained
from the ceramic media. As previous study by [16], the flocs on the
detrimental effect on the cyanide chalcopyrite flotation because of the
surface of chalcopyrite were the oxidized products from iron or copper,
formation of more oxygenated complex (Eqs. (4) and (5)), which is
which preferentially dissolved in the cyanide solution and strengthened
controlled by the strong mechanical forces and chemistry of the chal­
the etching reaction of chalcopyrite. In addition, the contact angle ex­
copyrite surface. Fig. 3(b) and Table 2 show the results of microflotation
periments showed that the grinding media affected the wettability of the
of cyanide chalcopyrite for the main elements (Cu, Fe and S) with
chalcopyrite surface (Fig. 2). This effect as shown in Fig. 5 continues into
different grinding media. Notably, the use of the iron media resulted in a
the cyanidation, causing a dramatic decline in the interface hydropho­
slight decrease in the copper grade, probably due to more chalcopyrite
bicity of chalcopyrite, which is more pronounced with the iron media.
reacting with cyanide and entering the solution. In addition, the reaction
EDS detection showed that Cu atoms concentration on the chalcopyrite
of iron oxides with cyanide produces ferrocyanide complexes, which is
surface decreased while the Fe atoms concentration increased after
for the reason why the flotation recovery of chalcopyrite obtained from
cyanidation for 24 h, and the use of iron media exacerbate this phe­
iron media after cyanidation is lower than from ceramic media.
nomenon compared to chalcopyrite before cyanidation (Fig. 2). The
CuFeS2 + 2CN- + 3OH- ⇄Cu(CN)-2 + FeOOH + 2S2- (7) decrease in the concentration of Cu atoms may be due to the reaction of
Cu with cyanide, resulting in the formation of an iron-rich surface. The
CuFeS2 + 10CN- ⇄Cu(CN)34- + Fe(CN)46- + 2S2- (8) increase in the concentration of Fe atoms is related to the reaction of
dissolved iron ions with hydroxide ions or cyanogen to form
2S2- + 2CN- + O2 + H2 O⇄2SCN-+ + 4OH- (9) iron-containing precipitates that reattach to the surface of the leaching
residue. The contact angle of chalcopyrite in the case of iron media
FeOOH + CN- ⇄Fe(CN)46- + 2OH
-
(10) decreased from 59.6◦ to 36.8◦ after cyanidation, while the contact angle
in the case of ceramic media decreased from 74.7◦ to 56.7◦ . This in­
Cu(OH)2 + 2CN- ⇄CuCN + 2OH- + 1/2(CN)2 ↑ (11) dicates that the floatability of leaching residue is affected by both
grinding media and cyanidation.
Cu+ + CN- ⇄CuCN (12)
3.4.2. XPS analysis
The survey scan spectra of cyanide leaching residue over a binding
3.3. Zeta potential analysis energy range of 1350 eV ~ 0 eV are presented in Fig. 6(a). No impurity
elements were found, except for the possible presence of air pollution C.
The variation in zeta potential on the samples surfaces at different pH N 1 s was detected on the surface of chalcopyrite obtained by ceramic
is shown in Fig. 4. The zeta potential values of chalcopyrite using media and iron media after cyanide leaching.
different grinding media after cyanide leaching have a similar trend in XPS high resolution spectra of C 1s, N 1s and O 1s of chalcopyrite
the range of pH 1–12. Compared with the zeta potential ground by using obtained by different grinding media after cyanide leaching are shown
ceramic media, the isoelectric point (IEP) of the samples by iron media in Fig. 6(b–d). The peak fit parameters are listed in Table 3. By using
moved to the left, indicating that the positive charges on the sample ceramic media, C 1s spectrum was fitted into three peaks positioned at

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Q. Zhao et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 644 (2022) 128799

Fig. 5. SEM (at different magnifications), EDS and contact angle images of cyanide leaching residue in 0.1% NaCN at T = 24 h: (A) ceramic media; (B) iron media.

Fig. 6. XPS results on the surface of cyanide leaching residue as a function of different pretreatment in 0.1% NaCN at T = 24 h: (a) survey scan spectra; (b) C 1s; (c) N
1s; (d) O 1s.

~284.57 eV, ~285.72 eV and ~289.47 eV, which could be assigned to galvanic couple action between the iron balls and the samples lead to
the bonds of C–C, C–O and C– – O, respectively (Fig. 6(b)) [30,31]. more copper sites on the surface of chalcopyrite to participate in the
However, the C 1s binding energy of chalcopyrite increased reaction. Fig. 6(d) is O spectra, which was fitted with the O 1s peaks. The
(~284.58 eV, ~286.13 eV, ~289.54 eV) in the case of iron media, peaks located at the energy of ~531.22 eV and 531.18 eV were attrib­
indicating that the loss of charge on the surface of the chalcopyrite. N 1s uted to Fe–OOH in the surface of samples, regardless of the grinding
peaks presented at ~397.80 eV and ~399.40 eV, which were assigned media [34]. Likewise, molecularly adsorbed oxygen also appeared on
to C–N / S–C–N and Cu–C–N, respectively (Fig. 6(c)) [32,33]. The the surface of chalcopyrite in the case of ceramic media and iron media
binding of Fe–C–N did not appeared on the surface of samples, which [21]. According to the above results, both ceramic and iron grinding
may be due to the substance is not easily adsorbed or Fe is not the active media could trigger the surface oxidation of chalcopyrite. The increase
site. The iron media results in a decrease in the percentage of C–N / in the formation of iron oxides on chalcopyrite surface confirms the
S–C–N, but an increase in the percentage of Cu–C–N, indicating that the contamination of iron media.

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Q. Zhao et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 644 (2022) 128799

Table 3
Fitting results of high resolution XPS spectra of C 1s, N 1s and O 1s on the chalcopyrite surface after 24 h cyanidation under different grinding media.
Peak Ceramic media Iron media

Comment B.E. (eV) Atomic (%) Comment B.E. (eV) Atomic (%)

C 1s C–C 284.57 78.41 C–C 284.58 81.06

C–O 285.72 17.83 C–O 286.13 12.93
C–
–O 289.47 3.76 C–
–O 289.54 6.01
N 1s C–N / S–C–N 397.83 68.86 C–N / S–C–N 397.80 25.94
Cu–C–N 399.41 31.34 Cu–C–N 399.40 74.06
O 1s Cu–O 529.60 14.49 Cu–O 529.57 11.42
Fe–OOH 531.22 71.81 Fe–OOH 531.18 78.51
molecularly adsorbed oxygen 533.44 13.70 molecularly adsorbed oxygen 532.89 10.07

Fig. 7. ToF–SIMS spectra on the surface of cyanide leaching residue as a function of different pretreatment in 0.1% NaCN at T = 24 h: (a) positive ion spectra, (b)
negative ion spectra.

3.4.3. ToF–SIMS analysis

Table 4
Fig. 7 shows the ToF–SIMS positive and negative mass spectra for the
Values of stability constants change at 298 K.
cyanide–treated chalcopyrite obtained using different grinding media in
the mass range m/z 0–200. For the positive mass spectra as shown in Central ions Metal cyanide complex Stability constant (log K)
Fig. 7(a), the representative peaks contained signals that originated from Cu+ CuCN 19.97
the C+, CH3+, C2H3+, C2H5+, C3H3+, C3H5+, C3H7+/C2H3O+ and C4H5+, Cu(CN)2− 16.09
all of which were fragments of adventitious carbonaceous species. In Cu(CN)32− 29.03
Cu(CN)43− 30.54
addition, Fe+ and Cu+ originated from the chalcopyrite, while the Fe+ Fe(CN)64− 35.40
FeSOH+ and FeSOCu+ were attributed to the CuFeS2 rearrangement. Fe(CN)63− 43.60
The presence of Na+ fragment regarded as cyanide (NaCN) adsorbed on
the chalcopyrite surface, which is consistent with XPS results (Fig. 7(a)).
The ToF–SIMS negative mass spectra are shown in Fig. 7(b). As with the level, while that of XPS is 1%. Furthermore, the type of cyanide
positive ion mass spectra results, fragments of the adventitious carbo­ adsorption and complexation on the chalcopyrite surface was not
naceous species also presented in the negative ion mass spectra, influenced by the grinding media. Notably, no ferricyanide complexes
including C–, CH–, CH2– and C2H–. The peaks that contain N should be were detected by either ToF-SIMS or XPS, which is inconsistent with the
related to cyanide fragments, such as, CN–, CNO–, SCN– and CuCN–. Eh-pH results of Yang et al. [15]. The main reasons for the above results
Moreover, the peaks for Cu(CN)2– and Cu(SCN)2– were clearly developed are as follows: (1) Cu and S on the chalcopyrite surface are the reaction
at m/z 115 and 176, respectively, which are inconsistent with the results sites that mainly react with CN–; (2) the ferricyanide complexes are not
of XPS. The reason for this inconsistency that ToF–SIMS and XPS may be easily attached to the chalcopyrite surface. Table 4 shows the stability
have different detection limit. The detection limit of ToF–SIMS is ppb constants of copper and iron-containing cyanide complex. The results
indicate that the stability constants of the ferricyanide complexes are

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Q. Zhao et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 644 (2022) 128799

Fig. 8. Normalized peak intensities on the surface of cyanide leaching residue as a function of different pretreatment in 0.1% NaCN at T = 24 h: (a) ToF-SIMS-
positive ions, (b) ToF-SIMS-negative ions.

higher than those of the copper-cyanide complexes. This finding has adsorption of xanthate negative ion collectors. As a result of all the
guiding significance for the selection of cyanide breakers for chalcopy­ above mentioned factors, chalcopyrite recovery was approximately
rite recovery from cyanide tailings. 5.55% higher in the case of grinding with ceramic media than that in the
The normalized peak intensities provide a wealth of information and case of grinding with iron media. A systematic experimental and
generally used to compare the abundance of species on the sample mechanistic analysis of the correlation between the cyanide adsorption
surface. Fig. 8 presents the normalized peak intensities of the main of chalcopyrite and the differences in grinding media was carried out.
positive and negative ions ToF- SIMS analysis after cyanidation of The efficient recovery of valuable resources from gold cyanide tailings
chalcopyrite obtained by different grinding media. As shown in Fig. 8 has significant economic, environmental and social benefits.
(a), the intensities of the normalized peaks of Cu+ and Fe+ on the
chalcopyrite surface were weak compared to Na+, a phenomenon CRediT authorship contribution statement
especially mentioned in the case of iron media. From Fig. 8(b), notably,
the use of ceramic media weakened (compared to iron media, the in­ Qianfei Zhao: Conceptualization, Data curation, Formal analysis,
tensity of the normalized peak intensity was reduce) the adhesion of Investigation, Methodology, Writing – original draft. Hongying Yang:
contaminants on the chalcopyrite surface, including CN–, CNO–, SCN–, Funding acquisition, Writing – review & editing. Linlin Tong: Funding
CuCN–, Cu(CN)2– and Cu(SCN)2–, inhibiting chalcopyrite flotation. The acquisition, Writing – review & editing. Ruipeng Jin: Data curation.
main reason for this phenomenon may be that the use of iron balls leads Pengcheng Ma: Writing – review & editing.
to an increase in the active sites on the chalcopyrite surface, resulting in
the production of more cyanide-containing contaminants, which in turn
affects the degree of contamination on the chalcopyrite surface and Declaration of Competing Interest
further flotation performance. Therefore, the use of ceramic media can
reduce the formation of contaminants at the source, which is of great The authors declare that they have no known competing financial
significance for the subsequent flotation recovery of chalcopyrite from interests or personal relationships that could have appeared to influence
cyanide tailings. the work reported in this paper.

4. Conclusion Acknowledgments

In this study, the influences of grinding media (ceramic media and This study was financially supported by National Key Research and
iron media) on the adsorption mechanism of cyanide to chalcopyrite Development Program of China (2018YFC1902001, 2018YFC1902002).
surface were investigated using multiple analytical techniques: We are very grateful to the Shandong Zhaojin Group co., Ltd.
SEM–EDS, contact angle, microflotation, zeta potential, XPS, and
ToF–SIMS. This work provides valuable insights into understanding the References
correlation of chalcopyrite surface oxidation, cyanide adsorption and
floatation behavior with different grinding media. In the process of iron [1] C. Anning, M.O. Asare, W. Junxiang, G. Yao, L. Xianjun, Effects of physicochemical
media grinding, due to the existence of the local cell and galvanic couple properties of Au cyanidation tailings on cyanide microbial degradation, J. Environ.
Sci. Health Part A Toxic Hazard. Subst. Environ. Eng. 56 (2021) 413–433, https://
action between iron media and chalcopyrite, the oxidation degree of the doi.org/10.1080/10934529.2021.1885259.
chalcopyrite surface is higher than that of the ceramic media. In addi­ [2] Y. Tu, P. Han, L. Wei, X. Zhang, B. Yu, P. Qian, S. Ye, Removal of cyanide adsorbed
tion, the oxygen/cyanide–containing, determined via XPS and on pyrite by H2O2 oxidation under alkaline conditions, J. Environ. Sci. 78 (2019)
287–292, https://doi.org/10.1016/j.jes.2018.10.013.
ToF–SIMS to be FeOOH, CN–, CNO–, CNS– and copper cyanide complex, [3] C. Lv, J. Ding, P. Qian, Q. Li, S. Ye, Y. Chen, Comprehensive recovery of metals
which had formed and scattered on the chalcopyrite surface, reducing from cyanidation tailing, Miner. Eng. 70 (2015) 141–147, https://doi.org/
the hydrophobicity of the chalcopyrite interface. Furthermore, the 10.1016/j.mineng.2014.09.007.
[4] H. Li, S. Li, P. Ma, Z. Zhou, H. Long, J. Peng, L. Zhang, Evaluation of a cleaner
contact angle of the chalcopyrite interface after cyanidation in the case production for cyanide tailings by chlorination thermal treatments, J. Clean. Prod.
of iron media dropped from 59.6◦ to 36.8◦ , while the contact angle of 281 (2021), 124195, https://doi.org/10.1016/j.jclepro.2020.124195.
chalcopyrite dropped from 74.7◦ to 56.7◦ because of the cyanide com­ [5] X. Yang, X. Huang, T. Qiu, Recovery of zinc from cyanide tailings by flotation,
Miner. Eng. 84 (2015) 100–105, https://doi.org/10.1016/j.mineng.2015.10.003.
plex formed. The left shift of IEP further confirmed that the accumula­
[6] G. Ai, H. Yan, T. Qiu, C. Liu, Activating flotation of chalcopyrite using CuSO4 and
tion of negative charge on chalcopyrite surface was not conducive to the H2O2 from the cyanide tailings, Physicochem. Probl. Miner. Process. 54 (2018)
578–589, https://doi.org/10.5277/ppmp1833.

8
Q. Zhao et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 644 (2022) 128799

[7] Q. Nie, M. Wang, T. Qiu, X. Qiu, Density functional theory and XPS studies of the [22] H. Lai, Q. Liu, J. Deng, S. Wen, Using ToF-SIMS to study metal ions transfer
adsorption of cyanide on chalcopyrite surfaces, ACS Omega 5 (2020) between chalcopyrite and galena during grinding, Adv. Powder Technol. 31 (2020)
22778–22785, https://doi.org/10.1021/acsomega.0c01739. 2650–2657, https://doi.org/10.1016/j.apt.2020.04.026.
[8] W. Yang, J. Ye, Y. Wang, T. Long, S. Deng, W. Xiao, K. Zhang, Regulation of lead [23] E. Díaz, L. Voisin, W. Kracht, V. Montenegro, Using advanced mineral
oxide on Cyaniding Behavior of chalcopyrite, Appl. Surf. Sci. 570 (2021), 151148, characterisation techniques to estimate grinding media consumption at laboratory
https://doi.org/10.1016/j.apsusc.2021.151148. scale, Miner. Eng. 121 (2018) 180–188, https://doi.org/10.1016/j.
[9] A.D. Bas, E. Koc, E.Y. Yazici, H. Deveci, Treatment of copper-rich gold ore by mineng.2018.03.015.
cyanide leaching, ammonia pretreatment and ammoniacal cyanide leaching, Trans. [24] A. Rabieh, J.J. Eksteen, B. Albijanic, Galvanic interaction of grinding media with
Nonferr. Met. Soc. China 25 (2015) 597–607, https://doi.org/10.1016/S1003- arsenopyrite and pyrite and its effect on gold cyanide leaching, Miner. Eng. 116
6326(15)63642-1. (2018) 46–55, https://doi.org/10.1016/j.mineng.2017.10.018.
[10] M. Adams, R. Lawrence, M. Bratty, Biogenic sulphide for cyanide recycle and [25] Y. Liu, C. Lv, J. Ding, P. Qian, X. Zhang, Y. Yu, S. Ye, Y. Chen, The use of the
copper recovery in gold-copper ore processing, Miner. Eng. 21 (2008) 509–517, organic-inorganic hybrid polymer Al(OH)3-polyacrylamide to flocculate particles
https://doi.org/10.1016/j.mineng.2008.02.001. in the cyanide tailing suspensions, Miner. Eng. 89 (2016) 108–117, https://doi.
[11] Z. Cao, P. Wang, W. Zhang, X. Zeng, Y. Cao, Mechanism of sodium sulfide on org/10.1016/j.mineng.2016.01.018.
flotation of cyanide-depressed pyrite, Trans. Nonferr. Met. Soc. China 30 (2020) [26] K. Dong, F. Xie, W. Wang, Y. Chang, D. Lu, X. Gu, C. Chen, The detoxification and
484–491, https://doi.org/10.1016/S1003-6326(20)65228-1. utilization of cyanide tailings: a critical review, J. Clean. Prod. 302 (2021),
[12] T. Qiu, X. Huang, X. Yang, Recovery of copper from cyanidation tailing by 126946, https://doi.org/10.1016/j.jclepro.2021.126946.
flotation, JOM 68 (2016) 548–555, https://doi.org/10.1007/s11837-015-1726-8. [27] Y. Kianinia, M.R. Khalesi, M. Abdollahy, G. Hefter, G. Senanayake, L. Hnedkovsky,
[13] X. Qiu, H. Yang, G. Chen, L. Tong, Z. Jin, Q. Zhang, Interface behavior of A.K. Darban, M. Shahbazi, Predicting cyanide consumption in gold leaching: a
chalcopyrite during flotation from cyanide tailings, Int. J. Miner. Metall. Mater. 29 kinetic and thermodynamic modeling approach, Minerals 8 (2018) 1–13, https://
(2020) 439–445, https://doi.org/10.1007/s12613-020-2170-5. doi.org/10.3390/min8030110.
[14] Y. Ma, Y. Han, Y. Zhu, Y. Li, H. Liu, Flotation behaviors and mechanisms of [28] J.H. Kyle, G. Hefter, A critical review of the thermodynamics of hydrogen cyanide
chalcopyrite and galena after cyanide treatment, Trans. Nonferr. Met. Soc. China and copper(I)-cyanide complexes in aqueous solution, Hydrometallurgy 154
26 (2016) 3245–3252, https://doi.org/10.1016/S1003-6326(16)64457-6. (2015) 78–87, https://doi.org/10.1016/j.hydromet.2015.03.012.
[15] X. Yang, X. Huang, T. Qiu, X. Jiao, Application of Eh-pH diagram for activation of [29] K. Quast, Literature review on the interaction of oleate with non-sulphide minerals
depressed chalcopyrite in cyanidation tailings, Miner. Process. Extr. Metall. Rev. 37 using zeta potential, Miner. Eng. 94 (2016) 10–20, https://doi.org/10.1016/j.
(2016) 134–138, https://doi.org/10.1080/08827508.2015.1115989. mineng.2016.04.016.
[16] Q. Zhao, H. Yang, L. Tong, Adsorption characteristics of CN− species on the [30] M. Ejtemaei, A.V. Nguyen, Characterisation of sphalerite and pyrite surfaces
chalcopyrite surface and its response to flotation, Sep. Purif. Technol. 276 (2021), activated by copper sulphate, Miner. Eng. 100 (2017) 223–232, https://doi.org/
119322, https://doi.org/10.1016/j.seppur.2021.119322. 10.1016/j.mineng.2016.11.005.
[17] Y. Peng, S. Grano, Effect of grinding media on the activation of pyrite flotation, [31] J. Liu, M. Ejtemaei, A.V. Nguyen, S. Wen, Y. Zeng, Surface chemistry of Pb-
Miner. Eng. 23 (2010) 600–605, https://doi.org/10.1016/j.mineng.2010.02.003. activated sphalerite, Miner. Eng. 145 (2020), 106058, https://doi.org/10.1016/j.
[18] Y. Peng, S. Grano, D. Fornasiero, J. Ralston, Control of grinding conditions in the mineng.2019.106058.
flotation of chalcopyrite and its separation from pyrite, Int. J. Miner. Process. 69 [32] G. Liu, Y. Huang, X. Qu, J. Xiao, X. Yang, Z. Xu, Understanding the hydrophobic
(2003) 87–100. mechanism of 3-hexyl-4-amino-1, 2,4-triazole-5-thione to malachite by ToF-SIMS,
[19] Y. Peng, S. Grano, D. Fornasiero, J. Ralston, Control of grinding conditions in the XPS, FTIR, contact angle, zeta potential and micro-flotation, Colloids Surf. A
flotation of galena and its separation from pyrite, Int. J. Miner. Process. 70 (2003) Physicochem. Eng. Asp. 503 (2016) 34–42, https://doi.org/10.1016/j.
67–82, https://doi.org/10.1016/S0301-7516(02)00153-9. colsurfa.2016.05.028.
[20] A. Azizi, S.Z. Shafaei, M. Noaparast, M. Karamoozian, The effect of pH, solid [33] A. Cano, Y. Avila, M. Avila, E. Reguera, Structural information contained in the
content, water chemistry and ore mineralogy on the galvanic interactions between XPS spectra of nd10 metal cyanides, J. Solid State Chem. 276 (2019) 339–344,
chalcopyrite and pyrite and steel balls, Front. Chem. Sci. Eng. 7 (2013) 464–471, https://doi.org/10.1016/j.jssc.2019.05.021.
https://doi.org/10.1007/s11705-013-1356-z. [34] X. Zhang, Y. Han, P. Gao, X. Gu, Y. Li, An investigation into the effects of grinding
[21] X. Zhang, Y. Han, P. Gao, Y. Li, Effects of grinding media on grinding products and media on grinding products characteristics and flotation performance of pyrite,
flotation performance of chalcopyrite, Miner. Eng. (2020), https://doi.org/ Miner. Process. Extr. Metall. Rev. 00 (2020) 1–7, https://doi.org/10.1080/
10.1016/j.mineng.2019.106070. 08827508.2020.1781629.