Minerals Engineering 121 (2018) 31–38

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Minerals Engineering
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Use of ZnSO4 and SDD mixture as sphalerite depressant in copper flotation T

a,b,⁎ a a b
Jian Liu , Yu Wang , Deqiang Luo , Yong Zeng
a
Faculty of Land Resource Engineering, Kunming University of Science and Technology, Kunming 650093, China
b
State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, China

A R T I C LE I N FO A B S T R A C T

Keywords: The depression performance and mechanism of the zinc sulfate (ZnSO4) and sodium dimethyl dithiocarbamate
Cu-Zn sulfide (SDD) combined depressant with butyl xanthate (BX) as collector in a mixed Cu-Zn sulfide floation system were
Flotation separation fully investigated using micro-flotation experiments, zeta-potential determination, and local electrochemical
Combined depressant impedance spectroscopy (LEIS) analysis. The micro-flotation experimental results indicated that the combined
Zeta-potential
depressant has a significant selective depression effect on sphalerite but has slight effect on chalcopyrite. The
LEIS
depression performance of the combined depressant strictly depends on the dosage of ZnSO4 + SDD and flo-
tation pH. However, excessive SDD is detrimental to chalcopyrite flotation. The optimum conditions for flotation
separation of chalcopyrite from the Cu-Zn sulfide were as follows: combined depressant dosage of 10−4 mol/L
(ZnSO4: SDD = 3:1), BX dosage of 10−5 mol/L, and flotation pH of 10. Under such conditions, a copper con-
centrate assaying 30.21% Cu with 86.79% recovery was achieved from the Cu-Zn sulfide flotation system, and
this concentrate had a very low Zn grade of 4.20% with 5.48% recovery. Both the zeta-potential and LEIS results
confirmed that the presence of the combined depressant can significantly prevent the adsorption of BX onto the
sphalerite surface, especially for an alkaline pH range of 9–12; however, the adsorption of BX onto the chal-
copyrite surface is not affected. The LEIS provides a powerful tool for observing the adsorption of flotation
reagents on mineral surface.

1. Introduction and Natarajan (2006)). One of the commonly used depressants in in-
dustrial processes is zinc sulfate (ZnSO4) in the presence of lime, the
As the most important minerals of copper and zinc, sphalerite (ZnS) depression mechanism of which is due to the formation of hydrophilic
and chalcopyrite (CuFeS2) always coexist with each other and form Cu- colloidal species such as HZnO2− and ZnO22− on the sphalerite surface
Zn sulfide ores. Most of the Cu-Zn sulfide ore is processed by differential (Cao and Liu, 2006). Another widely used depressant is sulph-oxy re-
flotation, in which chalcopyrite is floated first before sphalerite. agents such as sulfite, bisulfate, and most especially metabisulfite
Naturally, sphalerite has inferior floatability on its own, and the ad- (Grano et al., 1991). The depression mechanism of sulfite and bisulfate
sorption of ethyl xanthate to the sphalerite surface is weak (Chandra occurs through a chemical reaction that takes place with the hydro-
and Gerson, 2009; Finkelstein, 1999; Liu et al., 2014). However, the phobic species present on the mineral surface. Some researchers (Peres,
floatability of sphalerite can be increased significantly due to unin- 1979; Leja, 1982; Misra et al., 1985) suggested the formation of a metal
tentional activation by copper ions derived from the surface oxidation sulfite hydrophilic surface layer and consumption of copper ions in
and dissolution of chalcopyrite (Dávila-Pulido et al., 2011; Khmeleva solution by sulfite. Sulfite species interact with mineral sulfur species,
et al., 2005, 2006). As a result, a considerable amount of sphalerite can and this process may decrease the surface hydrophobicity. However,
float in the copper flotation circuit, causing a loss of zinc recovery. the depression performance of these common depressants, in most
Additional chemicals, so-called depressants, are generally required to cases, is not satisfactory in practice, especially for some complex Cu-Pb-
selectively depress sphalerite and achieve effective flotation separation Zn polymetallic sulfide ores. Recently, some researchers have tested
of chalcopyrite from the Cu-Zn sulfide ore. organic depressants to improve the flotation separation performance of
Normally, cyanide is the most effective depressant for the selective the polymetallic sulfide ore (Drzymala et al., 2003; Ekmekçi et al.,
depression of sphalerite from chalcopyrite during the froth flotation 2004; Liu et al., 2000; Qin et al., 2013; Sarquís et al., 2014). Sodium
process; however, the use of cyanide is strictly restricted due to its dimethyl dithiocarbamate (SDD, C3H6NS2Na) is the lowest homologue
potentially disastrous environmental consequences (Chandraprabha of dialkyldithiocarbamate salts, and it has the shortest hydrophobic

⁎
Corresponding author at: Faculty of Land Resource Engineering, Kunming University of Science and Technology, Kunming 650093, China.
E-mail address: vacation2008@126.com (J. Liu).

https://doi.org/10.1016/j.mineng.2018.03.003
Received 14 October 2017; Received in revised form 22 January 2018; Accepted 7 March 2018
0892-6875/ © 2018 Elsevier Ltd. All rights reserved.
J. Liu et al. Minerals Engineering 121 (2018) 31–38

group (eCH3) in its molecular structure with a weak hydrophobicity by atomic absorption spectrometry. The recovery of Cu and Zn was
(Qin et al., 2013). In preliminary exploration experiments, the com- calculated based on their contents in the concentrates and tailings.
bined use of conventional depressant ZnSO4 and SDD was found to have All the chemicals used in the experiments were chemically pure and
good selectivity for Cu-Zn sulfide flotation and achieved better se- purchased from Kunming Chemical Reagents Company. Cupric nitrate
paration performance than single use of ZnSO4 or SDD. However, the was used as activator. Hydrochloric acid and sodium hydroxide were
separation mechanism of Cu-Zn sulfide when using the ZnSO4 + SDD used for pH adjustment of acidic and alkaline solutions, respectively.
combined depressant has not been elucidated. Purely deionized water with a resistivity of 18 MΩ was produced with
In this work, the depression performance of the ZnSO4 + SDD the Milli-Q5O system (USA) and used throughout the experiments.
combined depressant in the mixed Cu-Zn sulfide flotation system with
butyl xanthate (BX) as collector was fully investigated. Moreover, the 2.3. Zeta-potential determination
depression mechanism of ZnSO4 + SDD was also investigated using
zeta-potential analysis and local electrochemical impedance spectro- The zeta potential was determined using a Malvern Zetasizer (Nano-
scopy (LEIS), which provides a powerful in situ examining of the sur- ZS900, Malvern Inc, UK) instrument, which requires a particle size less
face properties of substrates, such as surface defects, chemical adsorp- than 6 μm for the tested mineral. For each zeta-potential measurement,
tion, and surface reactivity (Jorcin et al., 2006; Taylor, 2001; Wittmann a mineral suspension (0.01% mass fraction) with appointed pH was
et al., 1999). added to a 50 mL glass reactor and followed by magnetically stirred
(500 rpm) for the desired time in the presence of the desired reagent
2. Materials and experimental method concentrations. Then, a moderate amount of mineral suspension was
transferred to the measurement vessel to determine the zeta-potential
2.1. Characterization of materials value at room temperature. The measurements were repeated three
times with the maximum standard deviation of ± 2.0 mV, and the
The materials used for the present study were natural pure spha- average value was recorded.
lerite and chalcopyrite. They were obtained from Yunnan Province,
China. They were soaked in 1% concentration of hydrochloric acid 2.4. LEIS experiments
solution for 1 h, cleaned by ultrasonication, and then air-dried. After
that, they were hand-ground with a mortar and pestle and sieved to The blocky sphalerite and chalcopyrite were cut and polished by
obtain a fraction with particle size of 40–75 μm. The chemical com- hand with wet silicon carbide paper in the sequence of 220, 400, 600,
positions of the materials are shown in Table 1. 800, and 1000 grit. Then, they were further polished with 5 μm of
According to Table 1, the sphalerite sample contained 63.68 wt% alumina powder suspensions. The freshly polished sphalerite and
Zn, 32.34 wt% S, 0.30 wt% Fe, and some minor Pb and SiO2 impurities. chalcopyrite substrates were ultrasonically washed in ethanol and Milli-
The chalcopyrite sample contained 33.79 wt% Cu, 29.82 wt% Fe, Q water for 5 min, respectively. The cleaned substrates were dried by
34.55 wt% S, 0.30 wt% Zn, and small amounts of Pb and SiO2. As a using highly pure N2. Then, the freshly prepared substrates were im-
result, the sphalerite and chalcopyrite samples reached a theoretical mediately transferred into a 1L electrochemical cell for LEIS experi-
purity of 96.02% and 98.16%, respectively. ments.
In addition, X-ray diffraction (XRD) (D/Max 2200, Rigaku, Japan) The LEIS experiments were performed on a scanning electro-
was used to further analyze the composition and crystal structure of the chemical workstation (Versa SCAN, AMETEK Inc, USA). A Pt dual-ele-
materials, with the result shown in Fig. 1. As shown in the figure, the ment probe with 5 μm radius was used as the LEIS tip. The tip was
sphalerite and chalcopyrite have a cubic (β-ZnS) and tetragonal struc- polished using a micro-polishing cloth with 0.05 μm alumina powder
ture, respectively. Although very small impurities were present in the suspension and rinsed thoroughly with ethanol and Milli-Q water be-
two samples, as shown in Table 1, they cannot be detected using XRD fore use. A freshly prepared substrate was mounted at the bottom of a
because of their very low content. LEIS cell with its surface exposed to the electrolyte solution. A Pt wire
was used as a counter electrode, and an Ag/AgCl electrode was used as
2.2. Micro-flotation test a reference electrode. It should be noted that in LEIS measurements, the
substrate does not need to be electrically connected to an external
The microflotation was carried out in a XFG flotation cell with an circuit, as required in traditional electro analytical techniques.
effective volume of approximately 40 mL in an open air condition. First, LEIS measurements were made from the ratio of the applied AC
the sphalerite and chalcopyrite were mixed with a proportion of 1:1, voltage to the local AC current density. The applied voltage (Vapplied)
and then 2.0 g of mixed sample was cleaned by ultrasonic treatment was the potential difference between the working electrode and the
prior to the flotation test. Afterward, the sample was mixed with 40 mL reference electrode. The local AC current density (Ilocal) was calculated
of distilled water. Conditioning was performed in the following order, using Ohm’s law:
depending on the number of reagents added: pH regulator, depressant, κVprobe
and collector. For each reagent addition, the conditioning time was set Ilocal =
d (1)
as 2 min. When a flotation experiment was completed, the products,
i.e., the concentrates and tailings, were collected from the flotation. The where κ is the conductivity of the electrolyte and Vprobe is the potential
collected flotation products were filtered, dried, and weighed. Finally, difference of Pt dual-element Probe; d is the distance between the two
the contents of Cu and Zn in the concentrates and tailings were assayed probes positioned on and in a conical plastic holder: one protrudes from
the tip of the cone and the other is a ring placed around the cone 3 mm
Table 1 from the tip. The local impedance Zlocal is calculated using Eq. (2):
Chemical compositions of materials.
Vapplied
Zlocal =
Sample Element content (wt%) Ilocal (2)
Cu Zn S Fe Pb SiO2 For local electrochemical impedance mapping, the probe was fixed
to approximately 50 μm above the sample surface, and stepped across a
Sphalerite – 63.68 32.34 0.30 0.65 < 0.50
Chalcopyrite 33.79 0.30 34.55 29.82 0.041 < 0.50 designated surface area of 0.4 × 0.4 mm with a step size of 20 μm in the
X and Y directions.

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J. Liu et al. Minerals Engineering 121 (2018) 31–38

Fig. 1. XRD results of the material.

3. Results and discussion SDD dosage was determined as 2.5 × 10−5 mol/L. Compared with
Fig. 3(a), the flotation separation performance of chalcopyrite and
3.1. Micro-flotation study sphalerite in the absence of ZnSO4 (Fig. 3(b)) was obviously inferior.
For example, the copper concentrate at the SDD dosage of
3.1.1. Effect of ZnSO4 and SDD dosage 3.5 × 10−5 mol/L had a Zn grade as high as 16.27% and Zn recovery of
In the case of the combined use of ZnSO4 and SDD, the dosage has a 30%. However, the copper concentrate at the same SDD dosage in the
significant influence on the depression performance of sphalerite in the presence of ZnSO4 had only Zn grade of 4.25% and Zn recovery of
mixed Cu-Zn sulfide flotation system. Thus, the dosage of ZnSO4 and 9.47%.
SDD was firstly investigated in the present study, with the results shown Combining the results of Figs. 2 and 3, the ZnSO4 and SDD mixture
in Figs. 2(a) and 3(a). In addition, the corresponding flotation control has an obviously better selective depression performance than that of
experiments with one depressant (ZnSO4 or SDD) were also performed single use of ZnSO4 or SDD. The optimal combination proportion for
to evaluate the effect of the mixture of ZnSO4 and SDD, with the results ZnSO4 and SDD is 3:1. It was noted that the dosage of SDD should be
shown in Figs. 2(b) and 3(b). strictly controlled and excessive SDD is detrimental to chalcopyrite
As shown in Fig. 2(a), ZnSO4 had an obvious selective depression flotation.
effect on the sphalerite in the flotation separation of chalcopyrite from a
mixed Cu-Zn sulfide flotation system and a negligible effect on chal-
copyrite flotation. The recovery and grade of zinc in copper concentrate 3.1.2. Effect of pH
decreased significantly with the increase of ZnSO4 dosage from After determining the optimal dosage of ZnSO4 and SDD, the effect
2.5 × 10−5 mol/L to 7.5 × 10−5 mol/L. However, the recovery and of pH on the separation performance of chalcopyrite and sphalerite was
grade of zinc decreased slowly with further increase of ZnSO4 dosage further investigated, and the result is shown in Fig. 4(a).
when the dosage exceeded 7.5 × 10−5 mol/L. As a result, the optimal As shown in Fig. 4(a), the depression performance of ZnSO4 and
ZnSO4 dosage was determined as 7.5 × 10−5 mol/L. At this dosage, a SDD on sphalerite strictly depends on the flotation pH. The depression
copper concentrate assaying 29.21% Cu with 83.79% recovery was performance increases significantly with the increase of pH, and it was
achieved from the Cu-Zn sulfide flotation system, and this concentrate better in alkaline conditions than in acidic conditions. Under a strong
had a low Zn grade of 8.20% with 12.48% recovery. As shown in acidic condition (pH = 4), the depression performance of ZnSO4 and
Fig. 2(b), the depression performance of sphalerite by single use of SDD on sphalerite was very weak. The optimal pH for separating
ZnSO4 in the absence of SDD was limited, and the optimal flotation chalcopyrite and sphalerite was pH = 10. Under this pH, a copper
separation index was achieved at the ZnSO4 dosage of 2.0 × 10−4 mol/ concentrate assaying 30.21% Cu with 86.79% recovery was achieved
L. However, under such ZnSO4 dosage, the copper concentrate had a from the Cu-Zn sulfide flotation system, and this concentrate had a very
lower Cu grade (24.73%) and a higher Zn grade (24.81%) than those of low Zn grade of 4.20% and Zn recovery of 5.48%. Fig. 4(b) shows the
the copper concentrate in the presence of SDD. results of the control experiment conducted at different pH values in the
As seen from Fig. 3(a), the recovery and grade of zinc in copper absence of depressant. As shown in the figure, the pH exerts a negligible
concentrate decreased significantly with the increase of SDD dosage influence on the depression of sphalerite in the mixed Cu-Zn sulfide
from 1.5 × 10−5 mol/L to 2.5 × 10−5 mol/L. When the dosage ex- flotation system, and effective depression of sphalerite could not be
ceeded 2.5 × 10−5 mol/L, the recovery and grade of zinc decrease achieved in the absence of depressant even at high alkaline pH. This
slowly. On the contrary, further increasing the SDD dosage decreased result was due to the fact that the floatability of sphalerite can be in-
the recovery and grade of copper, which indicated that excessive SDD creased significantly due to unintentional activation by copper ions
dosage is detrimental to chalcopyrite flotation. As a result, the optimal existing in the pulp of the Cu-Zn sulfide flotation system (Dávila-Pulido
et al., 2011; Khmeleva et al., 2005, 2006).

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J. Liu et al. Minerals Engineering 121 (2018) 31–38

Fig. 2. Effect of ZnSO4 dosage on the separation performance of chalcopyrite and sphalerite: (a) [SDD] = 2 × 10−5mol/L, [BX] = 1 × 10−5mol/L and pH = 10 (b)
[BX] = 1 × 10−5mol/L, pH = 10, and without SDD.

Fig. 3. Effect of SDD dosage on the separation performance of chalcopyrite and sphalerite: (a) [ZnSO4] = 7.5 × 10−5mol/L, [BX] = 1 × 10−5mol/L and pH = 10 (b)
[BX] = 1 × 10−5mol/L, pH = 10, and without ZnSO4.

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J. Liu et al. Minerals Engineering 121 (2018) 31–38

Fig. 4. Effect of pH on the separation performance of chalcopyrite and sphalerite: (a) [SDD] = 2.5 × 10−5 mol/L, [ZnSO4] = 7.5 × 10−5 mol/L and [BX] = 1 × 10−5 mol/L (b)
[BX] = 1 × 10−5mol/L, without depressant.

3.2. Zeta-potential analysis (5 × 10−6 mol/L) was used for zeta-potential measurement, and the
concentration of the other reagents was kept the same with the optimal
To illuminate the depression mechanism of ZnSO4 + SDD on spha- dose of flotation reagents used in Fig. 4(a).
lerite in the Cu-Zn sulfide flotation system, zeta-potential analysis was As shown in Fig. 5, the zeta potential of sphalerite after copper
performed on sphalerite and chalcopyrite after interaction with various activation is negative throughout the experimental pH range, which is
reagents, with the results shown in Figs. 5 and 6 respectively. Con- in good agreement with the study by Laskowski et al. (1997). The in-
sidering the fact that copper ions inevitably exist in the pulp of the Cu- crease of the sphalerite zeta potential after copper activation from pH 6
Zn sulfide flotation system, the sphalerite treated with Cu2+ to pH 10 is due to adsorption and precipitation of positive hydrolyzed

Fig. 5. Zeta potential of sphalerite after interaction with various reagents as a function of pH.

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J. Liu et al. Minerals Engineering 121 (2018) 31–38

Fig. 6. Zeta potential of chalcopyrite after interaction with various reagents as a function of pH.

Fig. 7. LEIS results of sphalerite surfaces after interaction with various reagents: (a) copper activation, AI = 1.23E+05 (b) ZnSO4 + SDD adsorption, AI = 1.28E+05 (c) BX adsorption,
AI = 1.31E+05. AI represents the average impedance of the tested area (0.4 mm × 0.4 mm).

copper ion species (Cu2(OH)22+ and Cu(OH)+) predominantly on the decreases significantly throughout the pH range, and this is due to the
sphalerite surface, whereas the decrease of zeta potential from pH 10 to adsorption of xanthate (X−) onto the sphalerite surface. As seen from
pH 12 results from the deprotonation of copper hydroxide that pre- Fig. 5, the Cu-activated sphalerite showed a remarkable increase in zeta
dominantly covered the sphalerite surface (Popov and Vučinić, 1990). potential after being conditioned with ZnSO4 + SDD in the pH range of
After being conditioned with BX further, the zeta potential of sphalerite 6–9. This result is attributed to the adsorption and precipitation of

36
J. Liu et al. Minerals Engineering 121 (2018) 31–38

Fig. 8. LEIS results of chalcopyrite surfaces after interaction with various reagents: (a) chalcopyrite surface, AI = 1.05E+05 (b) ZnSO4 + SDD adsorption, AI = 1.09E+05(c) BX
adsorption, AI = 1.15E+05. AI represents the average impedance.

positive hydrolyzed Zn ion species (Zn2(OH)22+ and Zn(OH)+) on the reaction processes, and the increase in the surface conductivity of the
Cu-activated sphalerite surface. Afterward, the zeta potential of the Cu- metal sulfides improves the surface reactivity and floatation response
activated sphalerite decreases sharply due to the vast adsorption of (Chen and Yoon, 2000; Tolley et al., 1996). The LEIS mapping results of
hydrophilic colloid species of Zn(OH)3− and Zn(OH)4− on the surface. the sphalerite and chalcopyrite substrate after interaction with various
After being conditioned with BX further, the sphalerite in the presence reagents are illustrated in Fig. 7 and Fig. 8, respectively.
of SDD and ZnSO4 has a smaller decreased zeta potential interval than As shown in Fig. 7(a), the surface of Cu-activated sphalerite is
that of sphalerite without SDD + ZnSO4, as denoted in the dashed circle mainly dominated by blue color, with average impedance (AI) of
in Fig. 5. This result indicated that the presence of SDD and ZnSO4 can 1.23 × 105. Compared with Fig. 7(a), the interaction of the sphalerite
significantly prevent the adsorption of BX onto the sphalerite surface, surfaces with the depressant ZnSO4 + SDD (Fig. 7(b)) and BX (Fig. 7(c))
especially for an alkaline pH range of 9–12. Such a result is in good leads to a remarkable increase in electrochemical impedance, with an
agreement with the observation in Fig. 4(a), i.e., the flotation of AI of 1.28 × 105 and 1.31 × 105, respectively. As seen from the green
sphalerite is apparently depressed in the presence of SDD + ZnSO4. color coverage area in Fig. 7(b), a large amount of ZnSO4 + SDD is
As shown in Fig. 6, whether the chalcopyrite was treated with or absorbed onto the Cu-activated sphalerite. However, further adsorption
without ZnSO4 + SDD, the adsorption of BX can result in a significant of BX onto the ZnSO4 + SDD covered sphalerite surface (Fig. 7(c)) is
decrease in zeta potential in the pH range of 9–12. The decreased zeta obviously restricted, and only a small amount of BX is absorbed onto
potential interval of chalcopyrite treated with or without ZnSO4 + SDD the surface. Moreover, some areas of the sphalerite surface did not
treatment is comparable with each other, as denoted in the dashed absorb BX.
circle in Fig. 6. This result indicated that the adsorption of BX onto the In order to contrast with the sphalerite, the adsorption of BX onto
chalcopyrite surface is not affected by the addition of depressant the chalcopyrite in the presence of ZnSO4 + SDD was also performed.
SDD + ZnSO4. This finding explains the excellent floatability of chal- Compared with Fig. 7(a), the chalcopyrite surface (Fig. 8(a)) has better
copyrite as observed in Fig. 4(a). conductivity (AI = 1.05 × 105) than the Cu-activated sphalerite surface
(AI = 1.23 × 105). It was indicated that chalcopyrite has excellent
surface reactivity and responds well to xanthate collectors. After in-
3.3. LEIS analysis of sphalerite and chalcopyrite surfaces teracting with the ZnSO4 + SDD combined depressant, the chalcopyrite
surface (Fig. 8(b)) exhibits an increase in electrochemical impedance,
The surface conductivity of Cu-Zn sulfide has a significant influence but the increased AI for chalcopyrite (△AI = 0.04 × 105) is less than
on the adsorption of various flotation reagents on its surface. This is due that for sphalerite (△AI = 0.05 × 105). This finding indicated that the
to the fact that such an activation and adsorption are electrochemical

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J. Liu et al. Minerals Engineering 121 (2018) 31–38

chalcopyrite surface absorbs less depressant ZnSO4 + SDD than the China (Grant Nos. 51764037 and 51704135), the University-Enterprise
sphalerite surface. As shown in Fig. 8(c), a large amount of BX is evenly Cooperation Fund from Yunnan Copper Group (Grant No.
absorbed onto the depressant-covered chalcopyrite surface, resulting in KKZ4201521003) and the Scholar Development Project of Yunnan
a significant increase in electrochemical impedance. The increased AI Province (Grant no. KKSY201421110) are sincerely appreciated.
for chalcopyrite(△AI = 0.06 × 105) after BX adsorption is double than
that for sphalerite (△AI = 0.03 × 105), which suggested that double References
amount of BX was absorbed onto the chalcopyrite surface.
Cao, M., Liu, Q., 2006. Reexamining the functions of zinc sulfate as a selective depressant
4. Conclusions in differential sulfide flotation—the role of coagulation. J. Colloid Interface Sci. 301,
523–531.
Chen, Z., Yoon, R.H., 2000. Electrochemistry of copper activation of sphalerite at pH 9.2.
It can be seen from the results and discussion above that: Int. J. Mineral Process. 58, 57–66.
Chandra, A.P., Gerson, A.R., 2009. A review of the fundamental studies of the copper
activation mechanisms for selective flotation of the sulfide minerals, sphalerite and
(1) The ZnSO4 + SDD combined depressant exerts an obvious selective pyrite. Adv. Colloid Interface Sci. 145, 97–110.
depression effect on the sphalerite in separating chalcopyrite from Chandraprabha, M.N., Natarajan, K.A., 2006. Surface chemical and flotation behaviour of
the mixed Cu-Zn sulfide flotation system. The depression perfor- chalcopyrite and pyrite in the presence of Acidithiobacillus thiooxidans.
Hydrometallurgy 83, 146–152.
mance of the combined depressant strictly depends on the dosage of
Dávila-Pulido, G.I., Uribe-Salas, A., Espinosa-Gómez, R., 2011. Comparison of the de-
ZnSO4 + SDD and flotation pH. However, excessive SDD is detri- pressant action of sulfite and metabisulfite for Cu-activated sphalerite. Int. J. Miner.
mental to chalcopyrite flotation. The depression performance in- Process. 101, 71–74.
Drzymala, J., Kapusniak, J., Tomasik, P., 2003. Removal of lead minerals from copper
creases significantly with the increase in flotation pH. Under acidic
industrial flotation concentrates by xanthate flotation in the presence of dextrin. Int.
conditions, the depression performance on sphalerite is very weak. J. Miner. Process. 70, 147–155.
(2) The optimum conditions for separating chalcopyrite from the mixed Ekmekçi, Z., Aslan, A., Hassoy, H., 2004. Effects of EDTA on selective flotation of sulphide
Cu-Zn sulfide were as follows: combined depressant dosage of minerals. Physicochem. Probl. Miner. Process. 38, 79–94.
Finkelstein, N.P., 1999. The activation of sulphide minerals for flotation: a review (vol 52,
10−4 mol/L (ZnSO4: SDD = 3:1), BX dosage of 10–5 mol/L and pg 81, 1997). Int. J. Miner. Process. 55, 283–286.
flotation pH of 10. Under such conditions, a copper concentrate Grano, S.R., Lauder, D.W., Johnson, N.W., Smart, R.St.C., Ralston, J., 1991. Comparison
assaying 30.21% Cu with 86.79% recovery was achieved from the of ethyl xanthate and diisobutyldithiophosphinate collectors for the lead roughing of
the Hilton ore of Mount Isa Mines Ltd. In: Fifth Extractive Metallurgy Conference.
Cu-Zn sulfide flotation system, and this concentrate had a very low Australasian Institute of Mining and Metallurgy Publisher, Parkville, pp. 203–210.
Zn grade of 4.20% with 5.48% recovery. Jorcin, J.B., Aragon, E., Merlatti, C., Pébère, N., 2006. Delaminated areas beneath organic
(3) The zeta-potential of sphalerite and chalcopyrite shows that the coating: a local electrochemical impedance approach. Corros. Sci. 48, 1779–1790.
Khmeleva, T.N., Chapelet, J.K., Skinner, W.M., Beattie, D.A., 2006. Depression mechan-
adsorption of ZnSO4 + SDD and BX leads to a remarkable increase isms of sodium bisulphite in the xanthate-induced flotation of copper activated
and decrease in zeta potential of the two minerals, respectively. The sphalerite. Int. J. Miner. Process. 79, 61–75.
presence of the ZnSO4 + SDD combined depressant can sig- Khmeleva, T.N., Skinner, W., Beattie, D.A., 2005. Depressing mechanisms of sodium bi-
sulphite in the collectorless flotation of copper-activated sphalerite. Int. J. Miner.
nificantly prevent the adsorption of BX onto the sphalerite surface,
Process. 76, 43–53.
especially for an alkaline pH range of 9–12. However, the adsorp- Laskowski, J.S., Liu, Q., Zhan, Y., 1997. Sphalerite activation: flotation and electrokinetic
tion of BX onto the chalcopyrite surface is not affected by the ad- studies. Miner. Eng. 10, 787–802.
Leja, J., 1982. Surface Chemistry of Froth Flotation. Plenum, New York, pp. 644–645.
dition of such depressant.
Liu, J., Wen, S.M., Deng, J.S., Chen, X.M., Feng, Q.C., 2014. DFT study of ethyl xanthate
(4) The LEIS results show that the adsorption of ZnSO4 + SDD com- interaction with sphalerite (1 1 0) surface in the absence and presence of copper.
bined depressant and BX results in a significant increase in elec- Appl. Surface Sci. 311, 258–263.
trochemical impedance, suggesting a decrease of surface reactivity. Liu, Q., Zhang, Y., Laskowski, J.S., 2000. The adsorption of polysaccharides onto mineral
surfaces: an acid/baseinteraction. Int. J. Miner. Process. 60, 229–245.
According to the increased AI value after depressant adsorption, Misra, M., Miller, J.D., Song, Q.Y., 1985. The effect of SO2 in the flotation of sphalerite
more combined depressant is absorbed onto the Cu-activated and chalcopyrite. In: Forssberg, K.S.E. (Ed.), Flotation of Sulphide Minerals,
sphalerite surface than that of the chalcopyrite surface. As seen Developments in Mineral Processing. Elsevier, Amsterdam, pp. 175–196.
Peres, A.E.C., 1979. The Interaction between Xanthate and Sulphur Dioxide in the
from the 3D LEIS mapping, the further adsorption of BX onto the Flotation of Copper–nickel Ores, PhD thesis, University of British Columbia.
combined depressant-covered sphalerite surface is obviously re- Popov, S.R., Vučinić, D., 1990. The ethylxanthate adsorption on copper-activated spha-
stricted, and only a small amount of BX is absorbed onto the sur- lerite under flotation-related conditions in alkaline media. Int. J. Miner. Process. 30,
229–244.
face. However, the adsorption of BX onto the combined depressant- Qin, W., Jiao, F., Sun, W., Wang, X.J., Liu, B., Wang, J., Zeng, K., Wei, Q., Liu, K., 2013.
covered chalcopyrite surface is not affected. Such result is in good Effects of sodium salt of N, N-dimethyldi-thiocarbamate on floatability of chalco-
agreement with the zeta-potential result. In addition, the increased pyrite, sphalerite, marmatite and its adsorption properties. Colloids Surf., A 421,
181–192.
AI for chalcopyrite(0.06 × 105) after BX adsorption is double than Sarquís, P.E., Menéndez-Aguado, J.M., Mahamud, M.M., Dziobac, R., 2014. Tannins: the
that for sphalerite (0.03 × 105), which suggested that double organic depressants alternative in selective flotation of sulfides. J. Clean. Prod. 84,
amount of BX was absorbed onto the chalcopyrite surface. 723–726.
Taylor, S.R., 2001. Incentives for using local electrochemical impedance methods in the
investigation of organic coatings. Prog. Org. Coat. 43, 141–148.
The present study contributes to the knowledge of efficiently se- Tolley, W., Kotlyar, D., Van Wagoner, R., 1996. Fundamental electrochemical studies of
parating chalcopyrite from mixed Cu-Zn sulfide ore and provides a new sulfide mineral flotation. Miner. Eng. 9, 603–637.
method for investigating the adsorption of flotation reagents on the Wittmann, M.W., Leggat, R.B., Taylor, S.R., 1999. The detection and mapping of defects
in organic coatings using local electrochemical impedance methods. J. Electrochem.
mineral surface. Soc. 146, 4071–4075.

Acknowledgements

Financial supports from the National Natural Science Foundation of

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