Selective flotation of galena from sphalerite using a combination of KMnO4 and

ed
carboxylated chitosan
Yuangan Chen1, 2, Bo Feng1, 2,*, Jinxiu Peng1, 2, Ziming Wang1, 2

1. Collaborative Innovation Center for Development and Utilization of Rare Metal Resources Co-

iew
sponsored by Ministry of Education and Jiangxi Province, Jiangxi University of Science and

Technology, Ganzhou 341000, China

2. Jiangxi Key Laboratory of Mining Engineering, Jiangxi University of Science and Technology,

Ganzhou 341000, China

v
* Corresponding author. E-mail addresses: fengbo319@163.com (B. Feng)

re
Abstract: An effective reagent combination plays a crucial role in the flotation
separation of galena and sphalerite. In this work, potassium permanganate (KMnO4)
was used to amplify the property difference between galena and sphalerite,
er
carboxylated chitosan (CCS) was used to selectively depress sphalerite. Artificial
mixed mineral experiment resulted in a Pb concentrate with a recovery of 97.77% and
pe
a grade of 72.90% Pb with 5 mg/L CCS and 1×10-4 mol/L KMnO4. The mechanism of
CCS in the separation of galena and sphalerite was investigated by microcalorimetric
measurements, X-ray photoelectron spectroscopy (XPS) and Fourier Transform
ot

Infrared (FTIR) Spectroscopy. The rate of sphalerite oxidation by KMnO4 is

significantly higher than galena, and more metal oxides will be produced on the surface
tn

of sphalerite. The metal oxides provided active sites for CCS to adsorb the sphalerite
surface via chemisorption, and the adsorption of CCS hindered the further adsorption
of potassium butylxanthate (PBX). However, the slow oxidation rate of galena results
rin

in less metal oxides produced, and CCS was mainly adsorbed on the surface of galena
with weak physical adsorption, which is easy to fall off, so the surface of galena will
continue to adsorb PBX. Thus, flotation separation of galena and sphalerite was
ep

achieved.
Key words: galena, sphalerite, KMnO4, carboxylated chitosan, flotation separation
Pr

Introduction
Lead and zinc are important non-ferrous metal raw materials and occupy an
extremely important position in the development of the national economy[1, 2]. Due to

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 the special and excellent physical and chemical properties of lead and zinc, its related

ed
products have been widely used in aerospace, electronics, military, chemical and
medical fields[3]. Galena and sphalerite are the main resources for the separation and
extraction of lead and zinc[4]. However, galena or sphalerite rarely exist independently,

iew
these ores are always tightly intertwined and difficult to separate[5, 6]. In addition, the
dissolved metal ions in the slurry solution will increase the difficulty of flotation
separation, especially Cu2+ adsorption on sphalerite surface could exchange the surface
zinc and enhance the interaction between the collector and the sphalerite surface, which

v
will activate the sphalerite and make galena and sphalerite similar in floatability[7-11].

re
Both galena and sphalerite are valuable minerals, so how to develop and separate them
efficiently and green is critical.
There is no doubt that flotation is a widely used and cost-effective method at
er
present for the separation of sulfide ores[12, 13]. Both galena and sphalerite activated
by Cu2+ could obtain higher recovery when xanthate is used as a collector. Therefore,
pe
it is interest to choose an appropriate depressant to separate galena and sphalerite
activated by Cu2+. Conventional inorganic depressants mainly include zinc sulfate, lime,
cyanide or their mixtures, but these depressants have the disadvantages of large dosage,
ot

high cost and are harmful to the environment[14]. Therefore, to reduce the cost of
beneficiation and reduce environmental pollution, organic polymer depressants have
tn

gradually entered the field of researchers due to their wide sources, environmental
friendly, and the ability to design functional groups according to mineral properties[2].
At present, the organic depressants of sulfide ore flotation include dextrin[15],
rin

polyaspartic acid[16], pectin[17], chitosan[18, 19] and some new synthetic reagents,
etc. Huang et al. used chitosan as a depressant to separate galena and sphalerite,
0.67mg/L chitosan could separate galena and sphalerite activated by Cu2+. The amino
ep

and hydroxyl groups in chitosan participate in the strong interaction with sphalerite[20].
Wang et al. used non-toxic and eco-friendly pectin to separate galena and sphalerite,
Pr

and the results showed that pectin was adsorbed on the surface of galena through
hydrophobic interaction and was easily replaced by xanthate, while pectin is chemically
complexed to Zn on the surface of sphalerite through its O atom on –OH and –

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 COOH[17]. Organic polymer reagents (e.g. chitosan, pectin) are difficult to dissolve,

ed
so it is difficult to achieve industrial application.
Carboxylated chitosan (CCS), also known as water-soluble chitosan, is the product
of the carboxylation reaction of amino or hydroxyl groups on the chitosan molecular

iew
chain[21]. CCS is widely used in medicine, chemical industry, biology, environmental
protection and other fields due to its excellent water solubility, moisture retention,
emulsification and biocompatibility. CCS molecular chain has a large number of
carboxyl groups. Due to the repulsion of the negative charge on the carboxyl group, the

v
polymer chain is stretched, and it is easy to complex with metal ions[22]. Coupled with

re
the hydrophilicity of the carboxyl group, it meets the requirements of lead and zinc
depressants. In this study, KMnO4 and CCS were used to separate galena and sphalerite,
and the oxidation law of galena and sphalerite was studied by microcalorimetry. The
er
adsorption mechanism of CCS on the surface of galena and sphalerite was studied by
FTIR spectroscopy and XPS.
pe
1. Experimental
1.1. Materials and reagents
The galena (PbS) lump and sphalerite (ZnS) lump used in this study were
ot

purchased from the Ye's mineral specimen group in Guangdong province, China. After
manual crushing, agate grinding and wet screening, the –74 +38 µm size fraction was
tn

used for flotation experiments and microcalorimetric measurements, and the –38 µm
size fraction was used for FTIR spectroscopy and XPS measurements. The results of
XRD analysis (Fig. 1) and Chemical analysis (Table 1) showed that galena and
rin

sphalerite are of high purity, and the purities of them were 97.82% and 96.09%,
respectively, suitable for flotation experiments and other surface measurements.
ep
Pr

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 Sphalerite
Galena
PDF#05-0566-Sphalerite-ZnS
PDF#05-0592-Galena-PbS

ed
iew
0 10 20 30 40 50 60 70 80 0 10 20 30 40 50 60 70 80

v
2(degree) 2(degree)

Fig. 1 XRD spectra of galena (a) and sphalerite (b).

re
Table 1 The chemical composition of galena and sphalerite
Sample S Pb Zn
Galena 13.11 84.71 -
31.56 - 64.38
Sphalerite
er
The collector potassium butylxanthate (PBX) was of industrial grade and obtained
from Nanjing Yinmao lead-zinc mine, Jiangsu Province, China. The biochemical
pe
reagent carboxylated chitosan (CCS) was purchased from Shanghai Aladdin
Biochemical Technology Co., Ltd. The frother methyl isobutyl carbinol (MIBC) and
spectrally pure potassium bromide (KBr) were purchased from Shanghai Macklin
ot

Biochemical Co., Ltd, Shanghai, China. The oxidant potassium permanganate

(KMnO4), pH regulators hydrochloric acid (HCl, 37%) and sodium hydroxide (NaOH,
tn

99%) were purchased from Xilong Science Co., Ltd, Shenzhen, China. The
experimental water comes from the ultrapure water machine model UPK-1-5T
produced by Sichuan Youpu Ultrapure Technology Co., Ltd., Sichuan Province, China.
rin

1.2. Micro-flotation experiments

Single mineral flotation experiment adopts XFGII5 flotation machine (Changchun
Prospecting Machinery Factory, Jilin Province, China), and the rotation speed was set
ep

to 1992 r/min. For each single mineral flotation experiment, 2 g mineral sample was
added to the flotation cell and ultrapure water was added to the 40 mL mark, and stirred
Pr

for 2 min to make it uniformly mixed. Then HCl or NaOH was used to adjust the pH of
the pulp to the desired value, when necessary, the CuSO4, KMnO4, CCS, PBX and

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 MIBC solution were added in sequence and stirred for 3 min, respectively. After various

ed
reagents were fully mixed with minerals, the flotation concentrate was collected for 3
min. Then the obtained concentrate and tailings were separately dried and weighed to
calculate the recovery. The final result was the average of three experiments. The

iew
artificial mixed minerals flotation experiment process was the same as the single
mineral flotation process. The recovery of artificially mixed minerals were calculated
by assaying the grade of the flotation forth product.
1.3. Microcalorimetric measurements

v
The microcalorimetric measurement was conducted using an RD496-2000

re
microcalorimeter manufactured by Mianyang Zhongwu Thermal Analysis Instrument
Co., Ltd., Sichuan Province, China. For each microcalorimetric measurement, weigh
0.05 g mineral sample and put it in the glass outer tube of the test pool, and add 1 mL
er
KMnO4 solution with concentration of 1×10-4 mol/L into the glass inner tube. First put
the glass inner tube into the glass outer tube, then put the outer tube into the stainless
pe
steel sleeve, and put it into the testing cell to be tested. Add the same quantity of mineral
samples to the glass outer tube in the reference pool, add 1 mL ultrapure water to the
inner tube, set the temperature parameter to 25 ℃, and when the baseline is stable,
ot

break the glass inner tube at the same time, and measure the thermodynamic parameters
of the reaction.
tn

1.4. XPS measurements

Thermo Scientific ESCALAB 250Xi X-ray Photoelectron Spectrometer was
applied to acquire XPS results and XPS software Thermo Advantage 5.9921 was
rin

utilized to fit and analyze the XPS peaks. All binding energies were referenced to the
standard C–C binding energy at 284.8 eV to compensate for the surface-charging
effects. The measurement samples were prepared in the following steps: 1g minerals
ep

were placed in a 100mL beaker, and then 40mL ultrapure water was added, adjust the
pH to 9, and then add 3×10-5 mol/L Cu2+, 1×10-5 mol/L KMnO4, 5 mg/L CCS, 1×10-4
Pr

mol/L PBX and 1×10-4 mol/L MIBC, stirred for 30 min. Then the pulp was filtered, and
the obtained samples were washed three times with ultrapure water, and then dried in a
vacuum drying oven at 40°C.

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 1.5. FTIR spectroscopy measurements

ed
The FTIR spectra were measured with an ALPHA FTIR spectrometer (Bruker,
Germany). The diffuse reflection method was used for the analysis, and the wavelength
measurement range was 500–4000 cm−1. The background spectrum was obtained using

iew
KBr powder. The preparation of the measurement sample is consistent with XPS
measurements.
2. Results and discussion
2.1. Micro-flotation experiments

v
To investigate the effect of CCS on the flotation behavior of galena and sphalerite,

re
single mineral flotation experiments were carried out first. It could be observed from
Fig. 2 that the depressive effect of CCS on galena and sphalerite is limited within the
experimental concentration range. When the concentration of CCS is lower than 100
er
mg/L, the recoveries of galena and sphalerite are both above 90%. When the quantity
of CCS was added to 200 mg/L, the depressive effect of CCS on sphalerite gradually
pe
appeared, but the flotation separation of galena and sphalerite was still unable to be
achieved.
100
ot

80
Recovery (%)

60 Galena
Sphalerite
tn

CPBX=1×10-4 mol/L
40
CMIBC=1×10-4 mol/L
CCu2+=3×10-5 mol/L
20 pH=7
rin

0
0 50 100 150 200
CCS concentrations (mg/L)

Fig. 2 Recovery of galena and sphalerite as function of CCS concentrations

Simply adding CCS cannot achieve flotation separation of galena and sphalerite.
ep

Adding an appropriate amount of KMnO4 could increase the difference in surface

properties between galena and sphalerite, which is helpful for separation[23]. As shown
Pr

in Fig. 3, the trace quantity of CCS treated with KMnO4 has a good depressive effect
on sphalerite, especially sphalerite. The sphalerite treated with KMnO4 could be well
depressed by 5 mg/L of CCS, but the depression effect of galena is not obvious. From

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 the single mineral flotation experiment results, 5 mg/L CCS could well achieve the

ed
flotation separation of galena and sphalerite treated with KMnO4, and continue to
increase the dosage of CCS will enhance the depression of galena, which is not
conducive to flotation.

iew
100

80 Sphalerite
Galena
CCu2+=3×10-5 mol/L
Recovery (%)

60 CKMnO4=1×10-5 mol/L
CPBX=1×10-4 mol/L

v
40 CMIBC=1×10-4 mol/L
pH=7

re
20

0
0 2 4 6 8 10
CCS concentration (mg/L)

Fig. 3 Recovery of galena and sphalerite in the presence of the KMnO4 as function of
CCS concentration.
er
Fig. 4 shows the effect of pH on the flotation behavior of galena and sphalerite
pe
treated with KMnO4 and CCS sequentially. Under acidic conditions, CCS has a weak
depressive effect on galena and sphalerite treated with KMnO4, and cannot achieve
flotation separation. Under neutral and weak alkaline conditions, sphalerite could be
well depressed, but galena has little effect. At pH > 9, the galena recovery decrease was
ot

that as the pH increases. It may be that the concentration of hydroxyl ions in solution
increases, which could eventually lead to the formation of metal hydroxides, and these
tn

may compete with the surfactant anion for adsorption sites on the particles. It is known
that hydroxides and metal oxides give hydrophilic character to the mineral surface and
rin

inhibit flotation, since they difficult the electrostatic interaction between the negatively
charged galena and the xanthate anions[24]. Therefore, neutrality and weak alkalinity
are the best conditions for flotation separation of galena and sphalerite using CCS.
ep
Pr

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 100

ed
80

Recovery (%)
60 Sphalerite
Galena
CCu2+=3×10-5 mol/L
40

iew
CKMnO4=1×10-5 mol/L
CCCS=5 mg/L
20 CPBX=1×10-4 mol/L
CMIBC=1×10-4 mol/L

0
2 4 6 8 10 12
pH

Fig. 4 Recovery of galena and sphalerite in the presence of the KMnO4 and CCS as

v
function of pH.

re
Single-mineral flotation experiments show that CCS could depress sphalerite
treated with KMnO4, but has little effect on galena. The pulp is a complex multiphase
system, and the mixed minerals flotation experiment could verify the separation effect
er
of the reagent in the interaction, which is more convincing. It could be seen from Fig.
5 that without depressant, the recovery of galena could reach 97.46%, but the Pb grade
pe
is only 52.3%, which cannot be separated. After adding 5 mg/L CCS, the recovery of
galena remained hardly changed, but the Pb grade reached 72.9%. Increasing the
quantity of CCS to 10 or 15 mg/L has little effect on improving the grade of Pb, but
significantly reduces the recovery of galena. It could be seen that the optimal dosage of
ot

CCS for separating galena and sphalerite is 5 mg/L.

100 100
tn

90 90
Recovery of galena
Grade of Pb
Recovery (%)

80 80
Grade (%)
rin

70 CCu2+=3×10-5 mol/L 70
CKMnO4=1×10-5 mol/L
CPBX=1×10-4 mol/L
60 60
CMIBC=1×10-4mol/L
pH=7
50 50
0 5 10 15
ep

CCS Concentration (mg/L)

Fig. 5 Flotation separation results of artificial mixed minerals as a function of CCS

concentration.
2.2. Microcalorimetric measurements
Pr

The difficulty of oxidation of galena and sphalerite could be judged by micro-

thermodynamic studies. Fig. 6 shows the heat rate curves of the reaction of galena and

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 sphalerite with KMnO4. The under-curve areas are the reaction heat effect value. It

ed
could be seen from Fig.6 that the thermal effect values of the reaction of galena and
sphalerite with KMnO4 are positive, indicating that the reaction is an exothermic
reaction. At the same time, it could be clearly seen that the under-curve areas of

iew
sphalerite were larger than that of galena.
12

10 Galena+KMnO4
Sphalerite+KMnO4
8
Heat flow (μW)

v
6

re
4

0 er1000 2000 3000 4000 5000 6000

t (s)

Fig. 6 Heat rate curves for the reaction of galena and sphalerite with KMnO4.
In order to more intuitively characterize the reaction rate, the thermal rate curve of
pe
the flotation time period was selected for the next analysis, and the rate coefficient was
calculated. The reaction between KMnO4 and sulfide ore could be approximated as an
irreversible redox reaction, and the rate coefficient K and reaction order n could be
ot

calculated by equation (1).

𝑙𝑛 [
] = 𝑙𝑛𝐾 + 𝑛𝑙𝑛[1 ‒ ]1 𝑑𝐻𝑖
𝐻∞ 𝑑𝑡 (1)
𝐻𝑖
𝐻∞
tn

The values of 𝑙𝑛[

1 𝑑𝐻𝑖
] are plotted as a function of [1 ‒ ], 𝑙𝑛𝐾 and 𝑛 are
𝐻∞ 𝑑𝑡
𝐻𝑖
𝐻∞

the intercept and slope of equation (1), respectively[25]. 𝑙𝑛[

1 𝑑𝐻𝑖
] and [1 ‒ ] 𝐻∞ 𝑑𝑡
𝐻𝑖
𝐻∞
rin

could be directly obtained from the historical record processing software of CK2000
microcalorimeter. Substitute into equation (1) to obtain the reaction order n and rate
coefficient K. The calculated results of the rate coefficient K for the reaction of KMnO4
ep

with galena and sphalerite are shown in Fig.7. Flotation is completed in a relatively
short time, so when adding KMnO4 for flotation, the oxidation rate of sphalerite was
Pr

significantly higher than that of galena. With the progress of the reaction, the surface
properties of galena and sphalerite gradually expanded, which not only weakened the
collection effect of PBX on sphalerite, but also promoted the adsorption of depressant

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 on the surface of sphalerite, which is beneficial to flotation separation[26, 27].

ed
0.0025

0.0020

Rate coefficients(s-1)
0.0015

iew
0.0010

0.0005 Sphalerite+KMnO4
Galena+KMnO4
0.0000

0 200 400 600 800 1000

t(s)

v
Fig. 7 Rate coefficients for the reaction of galena and sphalerite with KMnO4.
2.3. XPS analyses

re
XPS was conducted to analyze surfaces chemical species and to provide
quantitative surface-sensitive analysis of samples at various conditions. Fig. 8 presents
the XPS spectra of galena and sphalerite before and after CCS treatment. Due to the
er
small quantity of CCS, there is no visible change in the peaks in the full spectrum, but
it could be seen from the atomic content that the C content on the surface after being
pe
treated by CCS increases, indicating that CCS was adsorbed on the surface of galena
and sphalerite. In order to further analyze the adsorption mechanism between sulfide
ores and CCS, the high-resolution XPS of sphalerite and galena surfaces are shown in
ot

Fig. 9 and Fig. 10.

Sphalerite+Cu2++KMnO4 a Galena+Cu2++KMnO4
b
Zn 2p3

Pb 4f
tn

2+
Sphalerite+Cu +KMnO4+CCS Galena+Cu2++KMnO4+CCS
O 1s

C 1s

S 2p
Cu 2p3

O 1s

N 1s
C 1s

S 2p
N 1s
Intensity

Zn 2p3

Intensity

Pb 4f
O 1s

C 1s
rin Cu 2p3

O 1s

S 2p
C 1s

N 1s
S 2p
N 1s

Element Atomic/%
Element Atomic/%
CCS-untreate CCS-treate D-value
CCS-untreated CCS-untreated D-value d d
Zn 2p 60.48 60.47 -0.01 Pb 4f 49.52 49.13 -0.39
C 1s 16.06 16.91 0.85 C 1s 14.13 17.42 3.29
S 2p 8.17 8.09 -0.08 S 2p 17.68 15.54 -2.14
O 1s 15.29 14.53 -0.76 O 1s 18.67 17.71 -0.96

1200 1000 800 600 400 200 0 1200 1000 800 600 400 200 0
ep

Binding energy (eV) Binding energy (eV)

Fig. 8. The survey (full range) XPS spectra of sphalerite (a) and galena (b) surface
before and after treatment
Pr

The high-resolution S 2p spectra of sphalerite before and after being treated by

CCS are presented in Fig. 9(a), for S 2p spectrum of sphalerite before CCS treatment

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 could fit two doublets with binding energies of 161.56/162.76 eV and 161.78/163.04

ed
eV, which corresponding to ZnS and polysulfides, respectively. Compared to bare
sphalerite, the surface is oxidized to produce polysulfides[28, 29]. After the sphalerite
was treated with CCS, the peaks of the S 2p spectrum on the surface of the sphalerite

iew
did not shift significantly, indicating that the CCS did not act on the sulfur on the surface
of the sphalerite through chemisorption. In Fig. 9(b), the C 1s spectrum of CCS-
untreated sphalerite was divided into three peaks located at 284.80, 286.40 eV and
288.71 eV, representing C–C, C–O and C=O, respectively, attributed to adventitious

v
carbon contamination[30, 31]. According to the C 1s spectrum of CCS-treated

re
sphalerite, it is obvious that the area of the C–O peak at 286.33 eV has increased,
indicating that CCS is adsorbed on the surface. The O 1s spectra are presented in Fig.
9(c), for CCS-untreated sphalerite, the O1s spectrum is divided into three peaks with
er
binding energies at 529.99, 531.66 and 533.28 eV, the first two may be metal oxides
(e.g. Zn–O, SO42-) produced by the surface oxidation of sphalerite, and the latter may
pe
correspond to adsorbed water and hydroxides precipitated on the surface of sphalerite
[19, 32]. After being treated by CCS, a new peak with a binding energy of 531.22 eV
appeared on the O 1s spectrum, which may be originated from the C–O in the CCS
ot

molecule, indicating that CCS was adsorbed on the surface of sphalerite, while the
metal oxide located at 529.99eV was shifted to 530.79 eV, an increase of 0.80 eV. This
tn

indicated that the chemical environment of the metal oxides on the surface of sphalerite
has changed, and it is speculated that CCS is adsorbed on the metal oxides on the
surface of sphalerite through chemisorption.
rin
ep
Pr

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 Experiment line Experiment line (c) C 1s
(a) S 2p C–C
Polysulfide

ed
ZnS C–O
161.56 284.80
Background C=O
Fittig line 162.76 Background
Fitting line

163.04 161.78
286.40
288.71

iew
Sphalerite+Cu2++KMnO4 Sphalerite+Cu2++KMnO4

Experiment line Experiment line

Polysulfide C–C
161.53
ZnS C=O 286.80
Background C–O
Fitting line 162.74 Background
Fitting line

162.89 161.78 286.33

v
288.59

Sphalerite+Cu2++KMnO4+CCS Sphalerite+Cu2++KMnO4+CCS

re
168 166 164 162 160 158 300 298 296 294 292 290 288 286 284 282 280
Binding energy(eV) Binding energy(eV)

Experiment line (c) O 1s

Metal oxide
Metal oxide 531.66
Hydroxide/Adsorbed water
Background
Fitting line
er 529.99
533.28
pe
Sphalerite+Cu2++KMnO4

Experiment line
C–O/O–H
Metal oxide 531.93
Metal oxide
Hydroxide/Adsorbed water
Background 531.22
Fitting line
532.96 530.79
ot

Sphalerite+Cu2++KMnO4+CCS
544 542 540 538 536 534 532 530 528 526
tn

Binding energy(eV)

Fig. 9 S 2p (a), C 1s (b) and O 1s (c) spectra of sphalerite surface before and after
treatment.
Fig. 10(a) exhibits high-resolution C 1s spectra of galena surface before and after
rin

treated with CCS. For galena treated with KMnO4 only, the C1s spectrum was divided
into three peaks with binding energies of 284.80, 286.25 and 288.71 eV were assigned
ep

to C–C, C–O and C=O, respectively, attributed to adventitious carbon

contamination[30, 31]. For Galena treated with KMnO4 and CCS, the area under the
C–O peak at 286.33 eV increased significantly, indicating that CCS was adsorbed on
Pr

the surface. Fig. 10(b) shows the Pb 4f spectra of the galena surface with and without
CCS. The Pb 4f spectrum of galena surface treated with KMnO4 only divided into two

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 doublets, the doublets at 137.50/142.40 eV could be attributed to metallic Pb, another

ed
doublet at 138.58/143.48eV corresponds to oxidized Pb. Compared with the galena
untreated with KMnO4, the proportion of oxidized Pb on the surface of the galena
treated with KMnO4 increases, indicating that the galena surface was oxidized by

iew
KMnO4. The Pb 4f spectrum of galena surface with CCS divided into two doublets with
binding energies of 137.45/142.35 eV and 138.53/143.43 eV, representing metallic Pb
and oxidized Pb. It clearly shows that the proportion of oxidized Pb on the surface of
galena decreased after CCS treatment, which may be because CCS adsorbed on the

v
surface of galena to prevent oxidation or CCS covered the oxide on the surface of galena

re
and was not scanned. The O 1s spectra are presented in Fig. 10(c), for CCS-untreated
galena, the O1s spectrum is divided into three peaks with binding energies at 529.99,
531.33 and 532.32 eV, the first two may be cerussite-like phases and metal oxides
er
produced by the surface oxidation of galena, and the latter may correspond to adsorbed
water and hydroxides precipitated on the surface of galena[29, 33, 34]. After being
pe
treated by CCS, the proportion of hydroxide and adsorbed water increased, which may
be due to the adsorption of –OH in the CCS molecule to the Pb on the surface of galena,
and the binding energy of the two peaks was hardly shifted, it may be that the galena
ot

surface was hardly oxidized, and only a trace quantity of metal oxides could provide the
active sites for CCS chemisorption, mainly through weaker physisorption.
tn

Experiment line (a) C 1s Experiment line

C=O (b) Pb 4f
Metallic Pb 137.50
C–C 284.80 142.40
Oxidized Pb
C–O Background
Background Fitting line
Fitting line 138.58

143.48
288.71
rin

286.25

Galena+KMnO4 Galena+KMnO4

Experiment line
Experiment line
C=O
Metallic Pb
C–C 284.80 Oxidized Pb
ep

142.35 137.45
C–O Background
Background Fitting line
Fitting line

286.18
288.60 143.43 138.53
Pr

Galena+KMnO4+CCS
Galena+KMnO4+CCS
300 298 296 294 292 290 288 286 284 282 280 150 148 146 144 142 140 138 136 134
Binding energy(eV) Binding energy(eV)

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 Experiment line (c) O 1s
Hydroxide/Adsorbed water
Metal oxide

ed
Cerusite-like phases 531.33
Background
Fitting line

532.32 529.99

iew
Galena+KMnO4

Experiment line
Hydroxide/Adsorbed water
Metal oxide
Background
Fitting line 531.33

532.21

v
Galena+KMnO4+CCS

re
544 542 540 538 536 534 532 530 528 526
Binding energy(eV)

Fig. 10 C 1s (a), Pb 4f (b) and O 1s (c) spectra of galena surface before and after
treatment.
2.4. FTIR spectroscopy analyses
er
The XPS results show that CCS could be adsorbed on the surface of galena and
sphalerite. In order to further explore the separation mechanism of CCS, the FTIR
pe
spectra of galena and sphalerite under various conditions are shown in Fig. 11. In the
spectrum of CCS, the broad absorption peak at 3429 cm-1 corresponds to the stretching
vibration of the –OH, which may originate from the water absorbed by CCS[35, 36].
ot

The adsorption peaks at 1652 and 1579 cm-1 correspond to the asymmetric stretching
vibration of –COO– and the deformation vibration of N–H[37, 38]. The absorption peak
tn

at 1417 cm-1 corresponds to the symmetrical stretching vibration of –COO–, C–N

stretching vibration and N–H deformation vibration. The absorption peak in the range
of 1063~1154 cm-1 should come from the deformation vibration of C–O[37, 39]. In the
rin

spectrum of PBX, the adsorption peaks in the range of 2873~2957 cm-1 are attributed
to the stretching vibration of –CHn (e.g. –CH3, –CH2), while the range of 1368~1612
ep

cm-1 corresponds to the deformation vibration of –CHn. The peaks at 902~1190 cm-1
correspond to the stretching vibrations of C–O, C–S and C=S[40-42].
Fig. 11(a) shows the FTIR spectra of sphalerite under various conditions,
Pr

comparing the spectra before and after CCS treatment, the spectra of sphalerite treated
with CCS show a C–O adsorption peak at 1119 cm-1, with a strong intensity, which

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 may be due to the adsorption of CCS on the surface of sphalerite, while sphalerite

ed
continued to be treated with PBX did not show an obvious absorption peak of PBX,
which may be because the adsorbed CCS hindered the adsorption of PBX. From the
FTIR spectra, it could be concluded that CCS could be stably adsorbed on the surface

iew
of sphalerite, hindering the adsorption of PBX.
As shown in Fig. 11(b), galena treated without PBX have no obvious absorption
except for the –OH peak of adsorbed water and the –CHn peak brought by adventitious
carbon contamination. However, after treatment with PBX, obvious absorption peaks

v
appeared in the FTIR spectrum of galena in the range of 880-1094 cm-1, which may be

re
C–O, C–S and C=S in PBX. The FTIR spectra of galena under different conditions
showed that only a trace quantity of CCS was adsorbed on the surface of galena, and
the adsorption of CCS on the surface of galena is mainly through physisorption, which
er
is easy to be washed by water, while PBX could be stably adsorbed on the surface of
galena.
pe
a PBX
b
902

CCS
2852

1154
2963
2921

1115
1417

1063

902
3429

1579
1652

2873

1368

965
1467
1612
2935

Sphalerite+Cu2++KMnO4+CCS+PBX
3407

2957

1190

1066
ot

1115

Galena+KMnO4+CCS+PBX
1049
1121

880
1094
1053

Sphalerite+Cu2++KMnO4+CCS
Galena+KMnO4+CCS
1041
1119
tn

Galena+KMnO4
Sphalerite+Cu2++KMnO4

4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1) Wavenumber (cm-1)

Fig. 11 FTIR spectra of sphalerite(a) and galena(b) under various conditions.

rin

2.5. Discussion
It is a consensus that the surface oxidation of sulfide ore will weaken the collection
of xanthate[41, 43]. In addition, the flotation experiment shows that CCS has a weak
ep

depressing effect on galena and sphalerite without KMnO4 oxidation, while the
sphalerite oxidized by KMnO4 could be depressed by CCS, thereby realizing the
Pr

flotation separation of galena and sphalerite. It may be that the mineral surface was
oxidized by KMnO4 to change its surface properties, while the rate of KMnO4 oxidizing
sphalerite is significantly greater than galena. Combining to several surface analysis

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 technique results, it is inferred that there are a lot of metal oxides on the surface of

ed
sphalerite, so more CCS is firmly adsorbed on the metal oxides on the surface of
sphalerite through chemisorption, and the surface adsorption of CCS hinders the further
adsorption of PBX. While the surface of galena is slightly oxidized, there are not

iew
enough metal oxides to provide active sites for the chemisorption of CCS. Therefore,
the surface of galena mainly adsorbs CCS through weak physisorption, which is easily
washed away by water, so PBX could be smoothly adsorption on the surface of galena.
3. Conclusions

v
In this work, a combination of KMnO4 and CCS was used for the flotation

re
separation of galena and sphalerite. The feasibility of this scheme has been verified by
single mineral and artificial mixed minerals flotation experiments, and the adsorption
mechanism of CCS on sphalerite was delineated by several analysis techniques. The
er
key conclusions are summarized as follows:
(1) Micro-flotation experiments show that the combination of KMnO4 and CCS
pe
could effectively separate galena and sphalerite. A concentrate with a Pb grade
of 72.90% and recovery of 97.77% was obtained during the artificial mineral
mixture flotation experiment with 5 mg/L CCS and 1×10-4 mol/L KMnO4 at
ot

pH 7.
(2) The surface of galena and sphalerite is oxidized by KMnO4 at different rates,
tn

and sphalerite is easier to be oxidized. Therefore, KMnO4 could amplify the

differences in properties of galena and sphalerite surfaces
(3) CCS could be firmly adsorbed on the metal oxides adsorbed on the surface of
rin

sphalerite through chemisorption to hinder the adsorption of PBX, while the

surface of galena has a low oxidation rate and has not enough active sites for
CCS adsorption.
ep

4. Acknowledgments
This work was supported by Natural Science Foundation of China (52174248);
Pr

Natural Science Foundation of Jiangxi Province (20202ACBL214010); “Thousand

Talents Plan” of Jiangxi Province (jxsq2019201115); The Youth Jinggang Scholars
program in Jiangxi Province.

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 References

ed
[1] A.H.N. Kashani, F. Rashchi, Separation of oxidized zinc minerals from tailings:
Influence of flotation reagents, Miner Eng, 21 (2008) 967-972.
[2] B. Feng, C.H. Zhong, L.Z. Zhang, Y.T. Guo, T. Wang, Z.Q. Huang, Effect of

iew
surface oxidation on the depression of sphalerite by locust bean gum, Miner Eng, 146
(2020).
[3] B. Boryczko, A. Holda, Z. Kolenda, Depletion of the non-renewable natural
resource reserves in copper, zinc, lead and aluminium production, J Clean Prod, 84

v
(2014) 313-321.

re
[4] X.P. Huang, Y. Jia, Z.F. Cao, S. Wang, X. Ma, H. Zhong, Investigation of the
interfacial adsorption mechanisms of 2-hydroxyethyl dibutyldithiocarbamate surfactant
on galena and sphalerite, Colloid Surface A, 583 (2019).
er
[5] A.A. Baba, F.A. Adekola, Comparative analysis of the dissolution kinetics of galena
in binary solutions of HCl/FeCl3 and HCl/H2O2, Int J Min Met Mater, 18 (2011) 9-17.
pe
[6] J. Mei, Y. Liao, R.Y. Qin, P.X. Sun, C. Wang, Y.P. Ma, Z. Qu, N.Q. Yan, S.J. Yang,
Acceleration of Hg-0 Adsorption onto Natural Sphalerite by Cu2+ Activation during
Flotation: Mechanism and Applications in Hg-0 Recovery, Environ Sci Technol, 54
ot

(2020) 7687-7696.
[7] A.P. Chandra, A.R. Gerson, A review of the fundamental studies of the copper
tn

activation mechanisms for selective flotation of the sulfide minerals, sphalerite and
pyrite, Adv Colloid Interface, 145 (2009) 97-110.
[8] M. Ejtemaei, A.V. Nguyen, Characterisation of sphalerite and pyrite surfaces
rin

activated by copper sulphate, Minerals Engineering, 100 (2017) 223-232.

[9] J.Y. Wang, Q.X. Liu, H.B. Zeng, Understanding Copper Activation and Xanthate
Adsorption on Sphalerite by Time-of-Flight Secondary Ion Mass Spectrometry, X-ray
ep

Photoelectron Spectroscopy, and in Situ Scanning Electrochemical Microscopy, J Phys

Chem C, 117 (2013) 20089-20097.
Pr

[10] Y.Q. Li, J.H. Chen, Y. Chen, Y.G. Zhu, Y.C. Liu, DFT Simulation on Interaction
of H2O Molecules with ZnS and Cu-Activated Surfaces, J Phys Chem C, 123 (2019)
3048-3057.

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 [11] Z.Y. Gao, Z.Y. Jiang, W. Sun, Y.S. Gao, Typical roles of metal ions in mineral

ed
flotation: A review, T Nonferr Metal Soc, 31 (2021) 2081-2101.
[12] J.S. Deng, Y.B. Mao, S.M. Wen, J. Liu, Y.J. Xian, Q.C. Feng, New influence factor
inducing difficulty in selective flotation separation of Cu-Zn mixed sulfide minerals,

iew
Int J Min Met Mater, 22 (2015) 111-115.
[13] W.Z. Yin, Y. Tang, Interactive effect of minerals on complex ore flotation: A brief
review, Int J Min Met Mater, 27 (2020) 571-583.
[14] M.B. Hayat, L. Alagha, S.M. Sannan, Flotation Behavior of Complex Sulfide Ores

v
in the Presence of Biodegradable Polymeric Depressants, Int J Polym Sci, 2017 (2017).

re
[15] R.K. Rath, S. Subramanian, Adsorption, electrokinetic and differential flotation
studies on sphalerite and galena using dextrin, 57 (1999) 265-283.
[16] Q. Wei, F. Jiao, L.Y. Dong, X.D. Liu, W.Q. Qin, Selective depression of copper-
er
activated sphalerite by polyaspartic acid during chalcopyrite flotation, T Nonferr Metal
Soc, 31 (2021) 1784-1795.
pe
[17] C. Wang, R. Liu, W. Sun, N. Jing, Q. He, Selective depressive effect of pectin on
sphalerite flotation and its mechanisms of adsorption onto galena and sphalerite
surfaces, Minerals Engineering, 170 (2021) 106989.
ot

[18] C.T. Wang, R.Q. Liu, M.R. Wu, Q.L. Zhai, W. Sun, N.W. Jing, F.F. Xie, Induced
adsorption of pectin on copper-ion-modified galena surfaces: Flotation and adsorption
tn

mechanism, Miner Eng, 173 (2021).

[19] P. Huang, M.L. Cao, Q. Liu, Selective depression of sphalerite by chitosan in
differential Pb-Zn flotation, Int J Miner Process, 122 (2013) 29-35.
rin

[20] Peng, Huang, and, Mingli, Cao, and, Qi, Liu, Selective depression of sphalerite by
chitosan in differential PbZn flotation, International Journal of Mineral Processing,
(2013).
ep

[21] C.H. Lin, W.C. Li, T.T. Cheng, P.H. Wang, W.N. Lee, T.C. Wen, An investigation
of carboxylated chitosan hydrogel electrolytes for symmetric carbon-based
Pr

supercapacitors at low temperatures, J Taiwan Inst Chem E, 126 (2021) 324-331.

[22] A.S. Zhang, Y. Zhang, G.Y. Pan, J. Xu, H. Yan, Y.Q. Liu, In situ formation of
copper nanoparticles in carboxylated chitosan layer: Preparation and characterization

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 of surface modified TFC membrane with protein fouling resistance and long-lasting

ed
antibacterial properties, Sep Purif Technol, 176 (2017) 164-172.
[23] Y.H. Hu, M.R. Wu, R.Q. Liu, W. Sun, A review on the electrochemistry of galena
flotation, Miner Eng, 150 (2020).

iew
[24] M.A. Elizondo-Alvarez, G.I. Davila-Pulido, S. Bello-Teodoro, A. Uribe-Salas,
Role of pH on the adsorption of xanthate and dithiophosphinate onto galena, Can Metall
Quart, 58 (2019) 107-115.
[25] L.H. Lan, J.H. Chen, Y.Q. Li, P. Lan, Z. Yang, G.Y. Ai, Microthermokinetic study

v
of xanthate adsorption on impurity-doped galena, T Nonferr Metal Soc, 26 (2016) 272-

re
281.
[26] B. Feng, X.K. Jiao, H.H. Wang, J.X. Peng, G. Yang, Improving the separation of
chalcopyrite and galena by surface oxidation using hydroxyethyl cellulose as
er
depressant, Miner Eng, 160 (2021).
[27] Y.G. Chen, B. Feng, Y.T. Guo, T. Wang, L.Z. Zhang, C.H. Zhong, H.H. Wang,
pe
The role of oxidizer in the flotation separation of chalcopyrite and galena using sodium
lignosulfonate as a depressant, Miner Eng, 172 (2021).
[28] Y. Jia, Y. Zhang, Y.G. Huang, L.L. Chen, M. Wang, Y.L. Zhang, Synthesis of
ot

trimethylacetyl thiobenzamide and its flotation separation performance of galena from

sphalerite, Appl Surf Sci, 569 (2021).
tn

[29] H.Y. Zhu, B.Q. Yang, J.C. Feng, F.F. Jia, Evaluation of 1-hydroxyethylidene-1,1-
diphosphonic acid as an efficient and low-toxic sphalerite depressant in the selective
flotation of galena from sphalerite, J Clean Prod, 329 (2021).
rin

[30] H. Yan, B.Q. Yang, H.Y. Zhu, P.L. Huang, Y.J. Hu, Selective flotation of Cu-Mo
sulfides using dithiothreitol as an environmental-friendly depressant, Miner Eng, 168
(2021).
ep

[31] Z.G. Yin, W. Sun, Y.H. Hu, C.H. Zhang, Q.J. Guan, R.Q. Liu, P. Chen, M.J. Tian,
Utilization of acetic acid-[(hydrazinylthioxomethyl)thiol-sodium as a novel selective
Pr

depressant for chalcopyrite in the flotation separation of molybdenite, Sep Purif

Technol, 179 (2017) 248-256.
[32] Z.Z. Yang, L. Geng, H.P. Zhou, Z.S. Liu, F.X. Xie, S.Q. Yang, X.P. Luo,

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 Improving the flotation separation of chalcopyrite from galena through high-

ed
temperature air oxidation pretreatment, Miner Eng, 176 (2022).
[33] Z.W. Bao, T. Al, M. Couillard, G. Poirier, J. Bain, H.K. Shrimpton, Y.Z. Finfrock,
A. Lanzirotti, D. Paktunc, E. Saurette, Y.F. Hu, C.J. Ptacek, D.W. Blowes, A cross

iew
scale investigation of galena oxidation and controls on mobilization of lead in mine
waste rock, J Hazard Mater, 412 (2021).
[34] Z.G. Yin, W. Sun, Y.H. Hu, R.Q. Liu, W. Jiang, C.H. Zhang, Q.J. Guan, C.Y.
Zhang, Synthesis of acetic acid-[(hydrazinylthioxomethyl)thio]-sodium and its

v
application on the flotation separation of molybdenite from galena, J Ind Eng Chem, 52

re
(2017) 82-88.
[35] C.H. Zhong, B. Feng, L.Z. Zhang, W.P. Zhang, H.H. Wang, Z.Y. Gao, Flotation
separation of apatite and calcite using gum arabic as a depressant, Colloid Surface A,
er
632 (2022).
[36] Y.G. Chen, B. Feng, H.S. Yan, L.Z. Zhang, C.H. Zhong, T. Wang, H.H. Wang,
pe
L.H. Xu, Adsorption and depression mechanism of an eco-friendly depressant dextrin
onto fluorite and calcite for the efficiency flotation separation, Colloid Surface A, 635
(2022).
ot

[37] D.W. Yuan, K. Cadien, Q. Liu, H.B. Zeng, Adsorption characteristics and
mechanisms of O-Carboxymethyl chitosan on chalcopyrite and molybdenite, J Colloid
tn

Interf Sci, 552 (2019) 659-670.

[38] Y. Xiang, Carboxymethyl Chitosan as a Selective Depressant in Differential
Flotation of Galena and Chalcopyrite, 2015.
rin

[39] T. Wang, B. Feng, Y.T. Guo, W.P. Zhang, Y.B. Rao, C.H. Zhong, L.Z. Zhang, C.
Cheng, H.H. Wang, X.P. Luo, The flotation separation behavior of apatite from calcite
using carboxymethyl chitosan as depressant, Minerals Engineering, 159 (2020).
ep

[40] C.H. Zhong, H.H. Wang, L.Z. Zhang, M.C. Guo, B. Feng, Flotation separation of
molybdenite and talc by xanthan gum, Powder Technology, 388 (2021) 158-165.
Pr

[41] S.A. Khoso, Y.H. Hu, F. Lu, Y. Gao, R.Q. Liu, W. Sun, Xanthate interaction and
flotation separation of H2O2-treated chalcopyrite and pyrite, T Nonferr Metal Soc, 29
(2019) 2604-2614.

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179
 [42] S. Sadeghi, F.A. Rad, A.Z. Moghaddam, A highly selective sorbent for removal of

ed
Cr(VI) from aqueous solutions based on Fe3O4/poly(methyl methacrylate) grafted
Tragacanth gum nanocomposite: Optimization by experimental design, Mat Sci Eng C-
Mater, 45 (2014) 136-145.

iew
[43] D. Fornasiero, J. Ralston, Effect of surface oxide/hydroxide products on the
collectorless flotation. of copper-activated sphalerite, Int J Miner Process, 78 (2006)
231-237.

v
re
er
pe
ot
tn
rin
ep
Pr

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4116179