Physicochem. Probl. Miner. Process.

, 57(1), 2021, 294-304 Physicochemical Problems of Mineral Processing

ISSN 1643-1049
http://www.journalssystem.com/ppmp
© Wroclaw University of Science and Technology

Received October 25, 2020; reviewed; accepted December 29, 2020

Effect of compound phosphate collector on flotation separation of

jamesonite from marmatite and insights into adsorption mechanism
Weiqin Huang 1, Guohua Gu 1, Xiong Chen 2, 3, Yanhong Wang 1
1 School of Minerals Processing and Bio-engineering, Central South University, Changsha 410083, Hunan, China
2 Guangdong Institute of Resource Comprehensive Utilization, Guangzhou 510650, Guangdong, China
3 State Key Laboratory of Rare Metals Separation and Comprehensive Utilization, Guangzhou, 510650, Guangdong, China

Corresponding authors: guguohua@126.com (G. Gu), 155601016@csu.edu.cn (X. Chen)

Abstract: Separating jamesonite and marmatite is difficult due to their similar response to traditional
collectors. To improve the selectivity of the collector and simplify the reagent system, compound
phosphate (MP) as a collector for the separation of jamesonite from marmatite was studied in this study.
The flotation tests revealed that, compared with the most used butyl xanthate (BX), MP had the
advantages of lower dosage and stronger selectivity under weak acid pulp. Under the optimum
flotation conditions, a concentrate with the grade of 31.54% Pb, 6.93% Zn and the recovery of 89.87%
Pb, 12.31% Zn could be obtained from mixed binary minerals flotation (mass ratio of 1:1). Adsorption,
zeta potential, FT-IR and XPS analysis demonstrated that MP performed strong chemisorption on
jamesonite surface while underwent weak physisorption on marmatite, this difference was responsible
for the excellent selectivity of MP toward jamesonite flotation and weak collecting capacity to
marmatite.

Keywords: compound phosphate, jamesonite, marmatite, flotation separation, adsorption mechanism

1. Introduction
Jamesonite (Pb4FeSb6S14) is an important source of strategic metals lead and antimony (Reyes Perez et
al., 2019), which often coexists with other sulfide minerals, such as pyrrhotite (Fe1-xS), marmatite
((Zn,Fe)S), etc. (Radosavljevic et al., 2016) . Froth flotation is the most effective way to separate complex
sulfide ores, the difference in mineral surface hydrophobicity is the key to flotation separation (Wang,
2016). To modify the minerals surface properties, flotation reagents are added. Xanthates, as the
commonly used collector to enhance surface hydrophobicity of jamesonite, suffer from the
disadvantages of poor selectivity, so inhibitors are often used to inhibit marmatite in practice (Chen et
al., 2011; Wei et al., 2013). Therefore, it is necessary to find effective collectors with a superior selectivity
for the separation of jamesonite and marmatite. Some people have carried out relevant research on this
subject: Ma (Ma., 2006) used aromatic thiophenol collector to float jamesonite and marmatite and found
o-aminothiophenol and p-chlorophenylthiol exhibited stronger collecting ability for marmatite against
jamesonite; Sun (Sun et al., 2010) introduced a novel collector 2-aminothiophenol to separate marmatite
and jamesonite by the process of restraining lead and floating zinc; Wang (Wang, 2009) investigated the
effect of a new collector DT08 on the flotation behaviour of jamesonite and marmatite without copper
sulfate activation, and found that DT08 can realize the full flotation of two minerals under neutral
conditions. It can be concluded that the agents mentioned in the above studies have a strong ability to
collect marmatite rather than jamesonite. Usually, in the flotation process of polymetallic sulfide ore,
lead sulfide ore and zinc sulfide ore are separated in sequence (Öztürk et al., 2018; Chen et al., 2019),
which means that the above-mentioned collectors cannot be applied industrially. Hence, it is urgent to
find a collector with good collecting ability and strong selectivity for jamesonite to be suitable for the
industrial separation process of jamesonite and marmatite.

DOI: 10.37190/ppmp/132033
295 Physicochem. Probl. Miner. Process., 57(1), 2021, 294-304

In this study, a compound phosphate collector named MP was used to selectively separate
jamesonite from marmatite. MP is a compound phosphate collector composed of ammonium butyl
dithiophosphate, aniline dithiophosphate and sodium carbonate in the ratio of 1:1:1. MP contains –SH,
-P=S and -P-S2 functional groups, with strong collecting ability. Also, it is reported that -P=S and -P-S
can combine with Pb atom on the surface of galena to form strong chemical adsorption (Zhong et al.,
2015). Therefore, MP may be used for the flotation separation of jamesonite from marmatite in theory.
The flotation performance of MP was evaluated through micro-flotation tests of single minerals and
artificially mixed minerals. Moreover, zeta potential measurements, adsorption measurements, Fourier
transform infrared spectrum (FT-IR) and X-ray photoelectron spectra (XPS) were conducted to reveal
the adsorption mechanism of MP on jamesonite surface. The findings assist with new reagent selection
and theoretical support for promoting the flotation separation of jamesonite from marmatite.

2. Experimental
2.1. Materials and reagents
Pure jamesonite and marmatite samples were both obtained from Guangxi Province, China. The purity
of jamesonite and marmatite was over 98%, determined by chemical analysis and X-ray diffraction
analysis (XRD, Advance D8, Bruker Ltd., Switzerland) (Fig. 1). After crushing, grinding and screening,
the minerals with particle size of -75 to +38 µm were used for flotation tests. Minerals with particle size
less than 38 µm were used for zeta potential, FTIR and XPS analysis.
MP as collector was synthesized in the laboratory, which was composed of ammonium butyl
dithiophosphate, aniline dithiophosphate and sodium carbonate in the ratio of 1:1:1. Butyl xanthate (BX)
and Methyl isobutyl carbinol (MIBC) purchased from Zhuzhou Flotation Reagents Factory, Hunan
(China) were used as collector and frother, respectively. Analytical grade reagent sulfuric acid (H2SO4)
and sodium hydroxide (NaOH) were used as pH regulators. Deionized water was used for all
experiments.

Fig. 1. XRD patterns of (a) jamesonite and (b) marmatite

2.2. Methods
2.2.1. Flotation tests
Flotation tests were performed in an XFG-type flotation machine at a spindle speed of 1860 rpm. For
single mineral flotation tests, the sample (2.0 g) was cleaned by ultrasonication for 5 min, and then the
supernatant was discarded after standing for 5 min. Finally, the sample was flushed into a flotation cell
with 40 mL deionized water. The pulp pH was adjusted to the required value of 2, 4, 6, 8, 10, 12 by
adding diluted H2SO4 or NaOH solution. Then the collector and frother were added sequentially for
conditioning times of 3 and 1 min, respectively. Each flotation test was carried out for 3 min.
For artificially mixed minerals flotation tests, samples with 16.72 wt% Pb content consisted of pure
jamesonite and marmatite with a mass ratio of 1:1. Recovery was calculated on the basis of product
yields and Pb grades, which were assessed through chemical analysis.
296 Physicochem. Probl. Miner. Process., 57(1), 2021, 294-304

2.2.2. Zeta potential measurements

Malvern Zeta sizer Nano ZS90 (England) was used to measure the zeta potential. The suspension
consisting of 20 mg mineral sample with particle size less than 5 µm and 40 mL KCl electrolyte solution
(0.001 mol·L−1) was agitated by magnetic stirrer for 3 min. Afterwards, the suspension was conditioned
with or without MP at different pH values over the range of 2 to 12. The supernatant liquid was obtained
for measurement after 10 min of settling. Each sample was conducted at least three times, and the
averages were calculated as final results.

2.2.3. Adsorption measurements

The adsorption capacity was tested by TU-1810 UV–Vis spectrophotometer (Purkinje General, Beijing,
China). 2 g of mineral sample and 40 mL of distilled water were transferred to a 100 mL Erlenmeyer
flask. After adjusting the pH value of the slurry to the required test conditions, the collector MP was
added, then stirred with a magnetic mixer for 30 min to ensure the adsorption process had reached
equilibrium. After centrifugation of sample, the residual concentration of collector in the supernatant
was determined by UV spectrophotometry and the adsorption capacity was calculated.

2.2.4. FT-IR spectroscopy analysis

FT-IR spectroscopy was conducted with KBr as the background by a Spectrum One (version BM) FT-IR
(USA) spectrometer at 25°C. Purified minerals (1 g) were first ground to −2 µm, then conditioned with
MP at pH 5.5 for 40 min. After being filtered, the solid samples were washed three times using distilled
water, the samples were finally obtained by vacuum drying at 30 °C.

2.2.5. X-ray photoelectron spectroscopy (XPS) analysis

XPS analysis was carried out using k-alpha 1063 X-ray photoelectron spectrometer of Thermo Scientific
(UK). The preparation step of natural and treated jamesonite was consistent with that in flotation tests
tested at pH 5.5. The samples were filtered, washed three times by distilled water and vacuum dried at
30 °C. The final spectrums were calibrated by standard C 1s (BE=284.80 eV).

3. Results and discussion

3.1. Flotation tests for single minerals
3.1.1. Effect of pH on single minerals flotation recovery
The effect of pH on jamesonite and marmatite flotation recovery with (a) BX (b) MP as collector are
presented in Fig. 2 (a), (b), respectively. When using BX as collector, it can be seen from Fig. 2 (a) that
the recovery of both jamesonite and marmatite experienced a decrease with the increase of pH value. It
is worth mentioning that the recovery of jamesonite was higher than that of marmatite over the given
pH range, indicating that the floatability of jamesonite was better than that of marmatite. However, the
floatability difference was small at each pH value, the biggest deviation under pH 8.0, reaching 50%,

Fig. 2. Effect of pH on jamesonite and marmatite flotation recovery with (a) BX (b) MP as collector
297 Physicochem. Probl. Miner. Process., 57(1), 2021, 294-304

demonstrating that BX collector was not efficiently enough to selectively separate jamesonite from
marmatite. In this regard, we introduced a collector MP as an alternative to replace BX, and from Fig. 2
(b) it can be found that MP exhibited an excellent collecting ability and selectivity toward jamesonite
rather than marmatite. The recovery of jamesonite increased gradually and then reached a plateau at
pH around 5.5, reaching 95.46%. It can be noticed that the optimal pH range was between 4 and 6, a
further increase of pH above 6 would lead to a lower recovery. Compared to jamesonite, however,
marmatite maintained a rather low recovery around 7% throughout the pH range tested, which meant
that selectively separation of jamesonite and marmatite could be achieved using MP as collector.

3.1.2. Effect of collector dosage on single minerals flotation recovery

Fig. 3 shows the effect of collector dosage on the flotation of jamesonite and marmatite. The results of
Fig. 3 (a) meant that it was difficult to improve the flotation separation efficiency by adjusting BX
dosage. On the contrary, as shown in Fig. 3 (b), the recovery of jamesonite was 85% higher than that of
marmatite with increasing the dosage of MP until in excess of 10 mg/L, the recoveries of jamesonite
decreased dramatically from 92.45% to 46.25%. The recovery of jamesonite reached the maximum value
(95.18%) when the dosage of MP was 5 mg/L. The results indicated that low dosages of MP were
beneficial to the flotation of jamesonite.

Fig. 3. Effect of (a) BX (b) MP dosage on jamesonite and marmatite flotation recovery

3.2. Flotation tests for artificial mixed minerals

Based on single mineral flotation test results, MP was issued as a promising selective collector used for
the separation of jamesonite and marmatite. Therefore, the artificial mixed flotation tests were
performed to further evaluate the selectivity of MP with MP dosage fixed at 5 mg/L and pH as variable.
As shown in Fig. 4, under the premise of 16.72% Pb content of mixed minerals, the concentrate grade
of over 30% Pb with more than 89% recovery were obtained between pH 4.0 and 6.0. It is worth noting
that the grade and recovery of Zn fluctuated around 6% and 11% respectively, illustrating MP
selectively floated jamesonite in this pH range. Oppositely, ineffectively separation would be obtained
when pH exceeded this range, reflecting MP should be used under conditions of low MP dosage and
weak acid slurry.

3.3. Zeta potential analysis

Fig. 5 compares the zeta potential of jamesonite and marmatite in the presence or absence of MP at
various pH values. As shown in Fig. 5, the bare jamesonite surface was negatively charged within the
entire pH range tested and the isopotential point was not observed. In the presence of 5 mg/L MP, the
zeta potential of jamesonite shifted towards a more negative direction compared with that of raw ore,
which illustrated that electronegative MP was readily adsorbed onto the jamesonite surface. The
remarkable difference occurred at pH 2.0～6.0, indicating adsorption was more prominent at this range
which concurred with the flotation results. The zeta potential of untreated and MP-treated marmatite is
shown in Fig. 5. The isoelectric point (IEP) of marmatite differed in various literatures due to the diffe-
298 Physicochem. Probl. Miner. Process., 57(1), 2021, 294-304

Fig. 4. Separation results of jamesonite from marmatite under different pH

rence in the extent of oxidation of sample surfaces and the amount of iron present in solid solution (Lai
et al., 2019; Sui et al., 1998; Finkelstein, 1997; Zhang et al., 2014). Fig. 5 shows that the IEP of the pure
marmatite without any flotation reagents in aqueous solutions is observed to be around pH 2.7. With
the increase of pH value, the hydroxyl group adsorption on the metal sites was favoured, reducing the
zeta potential of marmatite from 3.9 mV (pH 2.0) to -46.4 mV (pH 12.0) (Davila-Pulido et al., 2014). After
MP treatment, the zeta potential only shifted slightly with increasing pH, indicating only a small
amount of MP was absorbed onto the marmatite surface over the whole pH range. This may be due to
the competitive adsorption of MP and hydroxide ions. The increment in the negative zeta potential
(∆|ζ|) has been directly related to adsorption density of the ions at the solid/water interface (Zhang et
al., 2014). It can be seen from Fig. 5 that the ∆|ζ| of jamesonite was throughout lager than that of
marmatite, which intuitively reflected that the adsorption density of MP on the jamesonite surface was
greater than that on marmatite surface.

Fig. 5. Zeta potentials of jamesonite and marmatite in the presence or absence of MP as a function of pH

3.4. Adsorption measurements results

The adsorption capacity of the agent is often used in combination with the zeta potential to characterize
the strength of the agent adsorption on the mineral surface. Fig. 6 shows the effect of pulp pH and MP
dosage on the adsorption of jamesonite and marmatite. Obviously, the adsorption capacity of MP on
jamesonite was much higher than that on marmatite, which was identical with the result of zeta
potential. It can be seen from Fig. 6 (a) that the adsorption of MP on the surface of jamesonite was highest
when the pH was 4.0～6.0, which indicates that MP prefers to adsorb in weak acid condition. As shown
in Fig.6 (b), the adsorption capacity on jamesonite increased correspondingly with the enlargement of
MP’s dosage. The growth rate was fast until the dosage increased to 10 mg/L, which could be explained
299 Physicochem. Probl. Miner. Process., 57(1), 2021, 294-304

by the weak alkalinity of MP. In other words, the pH value of the pulp rose when the dosage of MP
increased to a certain extent, exceeding the optimal pH range of 5.5～6.0 for jamesonite flotation (Lager
et al., 2015). Moreover, under the same conditions, regardless of the slurry pH value or MP dosage there
was little effect on MP adsorption of marmatite. It may be that the huge difference in adsorption capacity
of MP between jamesonite and marmatite results in its excellent selectivity. The difference in adsorption
capacity is related to the properties of mineral surface, which will be further analysed by FT-IR and XPS.

Fig. 6. Effect of (a) pH (b) MP dosage on the adsorption of jamesonite and marmatite

3.5. FT-IR spectra analysis

In Fig. 7 shows the FT-IR spectrum of MP. The characteristic adsorption peaks appearing at
2561.23 cm-1 and 2512.60 cm-1 were assigned to the stretching vibrations of –SH (Huang et al., 2010), and
stretching vibrations of –P=S occurred on 1276.24 and 840.12 cm-1 (Ignatkina et al., 2013; Zhang et al.,
2015). The peaks observed at 648.90 cm-1 and 542.78 cm-1 were attributed to the anti-symmetric
stretching vibrations of –P–S2 (Zhang et al., 2014). The peak at 3445.22 cm–1 was put down to
asymmetrical stretching vibration of -NH (Huang et al., 2010) and one peak located at 1493.56 cm−1
represented –CH3 or –CH2- deformation vibration (Zhang et al., 2014).

Fig. 7. FT-IR spectra of MP

To further understand the adsorption mechanism of MP, the FT-IR spectra of jamesonite and
marmatite before and after MP treatment are shown in Fig. 8. It is reported that if the characteristic
peaks of the reagent are not observed on the FT-IR spectrum of the mineral treated by the reagent, it
means that the adsorption of the agent on the mineral surface is very likely to be physical adsorption
(Zhao et al., 2019; Ming et al., 2020; Xiong et al., 2020). Conversely, if the characteristic peak of the
reagent appears in the FT-IR spectrum after the interaction between the reagent and the mineral, or the
wavenumber is shifted to a certain extent, it is considered that the chemisorption of the reagent on the
 300 Physicochem. Probl. Miner. Process., 57(1), 2021, 294-304

mineral surface has occurred (Zhao et al., 2021; Zhong et al., 2015; Cao et al., 2021). As shown in Fig. 8
(a), the characteristic peaks of bare jamesonite were observed at 977.35 cm-1 and 619.37 cm-1 (Sun et al.,
2015; Zhang et al., 2015). After interaction with MP, these peaks migrated to 997.62 and 651.43 cm-1,
respectively. Moreover, from the MP-treated jamesonite spectrum, some new peaks associated with MP
appeared at 1492.25 cm-1 (-CH3 or -CH2); 1146.72, 864.04 cm-1 (P=S); 587.59, 464.76 cm-1 (-P-S2). It can be
seen easily that the FT-IR spectrum of the jamesonite after conditioned with MP was basically consistent
with the FT-IR spectrum of lead dibutyl dithiophosphate reported in the literature, demonstrating MP
had strong chemisorption on jamesonite surface (Zhang et al., 2015). The main bands corresponding to
the relevant chemical bond of MP was summarized in Table 1, which was of great importance for
visually explaining the chemisorption between MP and jamesonite. As illustrated in Fig. 8 (b), the
characteristic peaks of bare marmatite appeared at 634.74, 798.21 and 1105.33 cm-1 (Wei et al., 2019).
After MP treatment, there were negligible changes on the spectra of marmatite, indicating MP was
weakly absorbed onto the marmatite surface. Therefore, we can reasonably speculate that physical
adsorption process may dominate the interaction of MP with marmatite. According to the results of FT-
IR spectra, it could be determined that MP had chemisorbed on jamesonite surface. However, for
marmatite, it can only be preliminarily judged that MP might be physically adsorbed on the marmatite
surface. Further analysis will be carried out through XPS, aiming to determine the atomic environment
223 based'RZQORDGVRXUFHILOH
8on the core-level binding
of 12 energy, to obtain the elemental
N% composition
Physicochem. andProcess.
Probl. Miner. chemical state of the
doi: xxx
interaction product of the MP with the mineral surface.

224 Fig.
Fig. 8. 8. FT-IR
FT-IR spectra
spectra of of
(a)(a)jamesonite
jamesonite(b)
(b) marmatite
marmatite before
beforeand after
and interacted
after with with
interacted MP MP

225
TableTable 1. The bands corresponding to the relevant chemical bond of MP in FT-IR spectra
1. The bands corresponding to the relevant chemical bond of MP in FT-IR spectra
226 FT-IR Band (cm-1) Chemical Bond Reference
FT-IR Band (cm-1) Chemical Bond Reference
227 3445.22 N-H (Huang et al., 2010)
228 3445.22
2561.23, 2512.60 N-H
S-H (Huang et al.,Zhang
(Ignatkina et al., 2013; 2010)et
229 2561.23, 2512.60 S-H (Ignatkina et al.,
al., 2015) 2013; Zhang et al.,
230 MP 1493.56 -CH3 or –CH2- (Zhang et al., 2014)
2015)
231 MP 1276.24,
1493.56840.12 -CH3P=S
or –CH2- (Huang
(Zhanget al.,
et 2010)
al., 2014)
232 648.90, 542.78
1276.24, 840.12 P-S
P=S2 (Zhang
(Huang et2014)
et al., al., 2010)
233 1492.25 -CH3 or –CH2- (Zhang et al., 2014)
648.90, 542.78 P-S2 (Zhang et al., 2014)
234 Jamesonite+MP 1146.72,864.04 P=S (Huang et al., 2010)
235 1492.25
587.59,464.76 -CH3P-S
or 2–CH2- (Zhang
(Zhang et2014)
et al., al., 2014)
Jamesonite+MP 1146.72,864.04 P=S (Huang et al., 2010)
236 3.6. XPS analysis 587.59,464.76 P-S2 (Zhang et al., 2014)
237 XPS is utilized to obtain more detailed information about the properties of minerals conditioned with
238 3.6. XPS
MP. analysis
Table 2 gives the XPS numerical data of jamesonite with and without MP pre-processing. It can be
239
XPS isseen that an
utilized elementmore
to obtain P with concentration
detailed 1.7% about
information appearsthein properties
the presenceof of MP, confirming
minerals conditioned the with
240 adsorption of MP on jamesonite surface.
MP. Table 2 gives the XPS numerical data of jamesonite with and without MP pre-processing. It can be
241
seen thatTable
an 2.element P with concentration 1.7% appears in the presence of MP, confirming the
Atomic concentration and binding energy of elements of jamesonite before and after MP treatment
adsorption of MP on jamesonite surface.
are prone Jamesonite
Phosphates Surface to interacting with heavy metal ions Jamesonite+MP
to form insoluble salts, making minerals
242 Atomic Binding Atomic Binding
hydrophobic and easy to float
elements (Zhang et al., 2015; Liu, 2009).concentration
concentration/% Energy/eV
To explore the interaction site of the surface
/% Energy/eV
243 C1s 25.7 284.80 23.2 284.80
244 O1s 10.3 530.44 9.2 530.39
245 S2p 33.7 161.26 34.2 161.09
246 Sb3d5 17.1 529.36 16.6 529.32
247 Pb4f 9.9 137.81 11.9 138.42
248 Fe2p 3.3 710.21 3.2 710.19
301 Physicochem. Probl. Miner. Process., 57(1), 2021, 294-304

Table 2. Atomic concentration and binding energy of elements of jamesonite before and after MP treatment

Jamesonite Jamesonite+MP
Surface
Atomic Binding Atomic Binding
elements
concentration/% Energy/eV concentration /% Energy/eV
C1s 25.7 284.80 23.2 284.80
O1s 10.3 530.44 9.2 530.39
S2p 33.7 161.26 34.2 161.09
Sb3d5 17.1 529.36 16.6 529.32
Pb4f 9.9 137.81 11.9 138.42
Fe2p 3.3 710.21 3.2 710.19
P2p - - 1.7 132.29

of jamesonite treated by MP, the high-resolution XPS of Pb 4f and Sb 3d were analysed. The change in
binding energy can judge whether metal elements participate in chemical reactions (Zhao et al., 2021).
As shown in Fig. 9 (A), the Pb 4f splits into Pb 4f7/2 and Pb 4f5/2 components. The peaks of Pb
4f7/2 spectrum of pure jamesonite at 137.81 eV and 138.78 eV correspond to Pb atom in Pb-S and Pb-O,
respectively (Ma et al., 2016; Jia et al., 2019). After interacting with MP, the binding energy of these two
peaks moved to 138.33 eV and 139.25 eV, respectively, indicating the electronic environment of the Pb
atom had been changed which might result from the donation of electrons by Pb to MP (Jia et al., 2019).
The result corroborated that MP reacted with Pb directly, which was in agreement with the result of FT-
IR analysis.
As presented in Fig. 9 (B), Sb 3d overlapped with O1s which was located at around 530.44 eV (Cao
et al., 2020). For pure jamesonite, the spectrum of Sb 3d5/2 was fitted into two peaks with binding
energy of 529.36 eV and 530.56 eV, which were assigned to Sb-S and Sb-O, respectively (Zakaznova-
Herzog et al., 2006). After adding MP, no new peak appeared and no significant shift occurred,
indicating Sb sites on the jamesonite performed very weak responsiveness towards MP adsorption.

Fig. 9. High-resolution XPS of (A) Pb4f (B) Sb3d ((a)jamesonite before and (b) after MP treatment)

Table 3 displays the surface properties of marmatite before and after MP treatment. After interaction
with MP, the relative atomic concentration of main elements C, Zn, O, S, on marmatite surface were
almost unchanged. The high-resolution XPS of Zn 2p3/2, S 2p of marmatite before and after MP
treatment were in Fig. 10 (A), (B). The spectrum of Zn 2p3/2 on the surface of fresh marmatite could be
divided into two peaks located at 1021.67 eV and 1022.58 eV, designated as Zn-S and Zn-O/OH,
respectively (Feng et al., 2020; Ejtemaei et al., 2017) . S 2p in pure marmatite was a typical doublet, and
species at binding energy of 161.69 eV and 162.89 eV were assigned to S2- of ZnS (Ejtemaei et al., 2017;
Huang et al., 2019). After MP treatment, Zn 2p3/2 and S 2p shifted only by + 0.01 eV, which were within
the instrumental error (0.2 eV), indicating that the adsorption between MP and marmatite was physical
302 Physicochem. Probl. Miner. Process., 57(1), 2021, 294-304

instead of chemical (Pan et al., 2020; Liu et al., 2020; Cao et al., 2020). These results were in good
agreement with the FT-IR results.
Based on FT-IR and XPS analysis, the results demonstrated that MP exhibited strong chemisorption
on the jamesonite surface due to lead sites readily combine with MP, which had a positive effect on the
jamesonite flotation. However, the negligible change in the binding energy of Zn indicated that Zn sites
on the surface of marmatite were not sensitive to MP adsorption, which further corroborated MP was
adsorbed on marmatite surface by weak physical adsorption.

Table 3. Atomic concentration and binding energy of elements of jamesonite before and after MP treatment

Marmatite Marmatite +MP

Surface
Atomic Binding Atomic Binding
elements
concentration/% Energy /eV concentration /% Energy /eV
C1s 27.9 284.80 26.7 284.80
O1s 12.2 531.67 12.3 531.65
S2p 28.7 161.71 29.5 161.72
Fe2p 7.0 709.78 7.1 709.75
Zn2p3 24.2 1021.67 24.4 1021.66

Fig. 10. High-resolution XPS of (A) Zn 2p3/2 (B) S 2p ((a)marmatite before and (b) after MP treatment)

4. Conclusions
Compound phosphate (MP) was employed as a collector in the flotation separation of jamesonite from
marmatite without any depressant. Micro-flotation results showed that MP had the advantages of lower
dosage and better selectivity than conventional collector BX. When MP dosage was 5 mg/L, the mixed
minerals containing 16.72% Pb could be effectively separated with a Pb concentrate grading over 30%
at a recovery of close to 90% under the weak acid pH range (4.0 to 6.0).
In addition, it is concluded from zeta potential, adsorption, FT-IR and XPS analysis that MP strongly
adsorbed on jamesonite surface under weak acidity, while slightly adsorbed on marmatite surface in
the whole pH. The interaction between MP and jamesonite was governed primarily by chemisorption,
whereas that between MP and marmatite mainly occurred through weak physical adsorption. This is
the reason why MP has excellent selectivity for jamesonite and poor collecting ability to marmatite. The
research has important significance for the processing of lead-zinc ores.

Acknowledgments
The authors acknowledge the support of the National Key Technology R&D Program
(No.2015BAB12B02); National Natural Science Foundation of China (No.52074358); GDAS’ Project of
Science and Technology Development (2020GDASYL-20200103104).!
303 Physicochem. Probl. Miner. Process., 57(1), 2021, 294-304

References
REYES, PEREZ, M., PALACIOS, BEAS, E.G., BARRIENTOS, F.R., PEREZ, LABRA, M., JUAREZ, TAPIA, J.C.,
REYESDOMINGUEZ, I.A., FLORES GUERRERO, M.U., TEJA, RUIZ, M.A., GUTIERREZ, GARCIA, C.E., 2019.
Chemical and Instrumental Characterization of a Sulphosalt Lead Type Jamesonite, Minerals Metals & Materials Series,
503-510.
RADOSAVLJEVIC, S.A., STOJANOVIC, J.N., RADOSAVLJEVIC-MIHAJLOVIC, A.S., VUKOVIC, N.S., 2016. (Pb-
Sb)-bearing sphalerite from the Cumavici polymetallic ore deposit, Podrinje Metallogenic District, East Bosnia and
Herzegovina, Ore. Geol. Rev, 72(1), 253-268.
WANG, G., 2016. Mode-independent control of singular Markovian jump systems: A stochastic optimization viewpoint,
Appl. Math. Comput, 286, 155-170.
CHEN, J., LI, Y., LONG, Q., WEI, Z., CHEN, Y., 2011. Improving the selective flotation of jamesonite using tannin extract,
Int. J. Mineral Process, 100(1-2), 54-56.
WEI, Z., WU, C., YU, Z., HUANG, R., MU, X., 2013. Research The Several Organic Inhibitors Influence On Jamesonite
And Marmatite, Adv. Mat. Res, 275, 616-618.
MA, G., 2006. Study on flotation property of Pb-Sb-Zn-Fe sulfide by aryl thiolate collectors. Doctoral dissertation,Central
South University.
HUANG, H., SUN, W., 2010. Effect of 2-aminothiophenol on the separation of jamesonite and marmatite, Min. Sci. Technol,
20(3), 425-427.
WANG, J., Investigation on the new collector for the bulk-flotation of multy-metal sulfideore in Dachang. Doctoral
dissertation, Guangxi University.
ÖZTÜRK, Y., BLÇAK, Ö., ÖZDEMIR, E., EKMEKÇI, Z., 2018. Mitigation negative effects of thiosulfate on flotation
performance of a Cu-Pb-Zn sulfide ore, Miner. Eng, 122, 142-147.
CHEN, W., CHEN, T., BU, X., CHEN, F., DING, Y., ZHANG, C., DENG, S., SONG, Y., 2019. The selective flotation of
chalcopyrite against galena using alginate as a depressant, Miner. Eng, 141,148-105.
ZHONG, H., HUANG, Z., ZHAO, G, WANG, S., LIU, G., CAO, Z., 2015. The collecting performance and interaction
mechanism of sodium diisobutyl dithiophosphinate in sulfide minerals flotation, Mater. Res. Technol, 4(2), 151-
161.
LAI, H., DENG, J., WEN, S., LIU, Q., 2019. Elucidation of lead ions adsorption mechanism on marmatite surface by PCA-
assisted ToF-SIMS, XPS and zeta potential. Miner. Eng, 144, 106035.
SUI, C., RASHCHI, F., XU, Z., KIM, J., NESSET, J.E., FINCH, J.A., 1998. Interactions in the sphalerite-Ca-SO4-CO3
systems. Colloids Surf, 137(1–3), 69-77.
FINKELSTEIN, N.P., 1997. The activation of sulphide minerals for flotation: a review. Int. J. Mineral Process, 52(2-3), 81-
120.
ZHANG, T., QIN, W., YANG, C., HUANG, S., 2014. Floc flotation of marmatite fines in aqueous suspensions induced by
butyl xanthate and ammonium dibutyl dithiophosphate, Trans. Nonferrous Met. Soc. China, 24(5), 1578-1586.
ZHAO, L., LIU, W., DUAN, H., WANG, X., FANG, P., LIU, W., ZHOU, X., SHEN, Y., 2021. Design and selection of
flotation collectors for zinc oxide minerals based on bond valence model. Miner. Eng, 160, 106681.
CAO, Y., XIE, X., TONG, X., FENG, D., LV, J., CHEN, Y., SONG, Q., 2021. The activation mechanism of Fe(II) ion-
modified cassiterite surface to promote salicylhydroxamic acid adsorption. Miner. Eng, 160, 106707.
DAVILA-PULIDO, G. I., URIBE-SALAS, A., G.I. 2014. Effect of calcium, sulphate and gypsum on copper-activated and
non-activated sphalerite surface properties. Miner. Eng, 55(1), 147-153.
IGNATKINA, V.A., BOCHAROV, V.A., D'YACHKOV, F.G., 2014. Collecting properties of diisobutyl dithiophosphinate
in sulfide minerals flotation from sulfide ore. J. Min. Sci., 49(5), 795-802.
LAGER, T., FORSSBERG, E., 2015.Beneficiation characteristics of antimony minerals.
SUN, W., HAN, H., TAO, H., LIU, R., 2015. Study on the flotation technology and adsorption mechanism of galena-
jamesonite separation, Int. J. Min. Sci. Technol, 25(1), 53-57.
ZHANG, T., QIN, W., 2015. Floc flotation of jamesonite fines in aqueous suspensions induced by ammonium dibutyl
dithiophosphate, J. Cent. South Univ, 22(4), 1232-1234.
WEI, Q., JIAO, F., QIN, W., DONG, L., FENG, L., 2019. Use of PASP and ZnSO4 mixture as depressant in the flotation
separation of chalcopyrite from Cu-activated marmatite, Physicochem. Probl. Miner. Process, 55(5), 1192-1194.
ZHAO, K., WANG, X., WANG, Z., YAN, W, ZHOU, X., XU, L., WANG, C., 2019. A novel depressant for selective
flotation separation of pyrite and pyrophyllite, Appl. Surf. Sci, 487, 9-13.
304 Physicochem. Probl. Miner. Process., 57(1), 2021, 294-304

MING, P., XIE, Z., GUAN, Y., WANG, Z., LI, F., XING, Q., 2020. The effect of polysaccharide depressant xanthan gum
on the flotation of arsenopyrite from chlorite, Miner. Eng, 157, 106551.
XIONG, W., DENG, J., ZHAO, K., WANG, W., WANG, Y., WEI, D., 2020. Bastnaesite, Barite, and Calcite Flotation
Behaviors with Salicylhydroxamic Acid as the Collector, Miner, 10, 282-286.
MAN, X., OU, L., WANG, C., JIN, S., MA, X., 2019. Flotation Separation of Diaspore and Kaolinite by Using a Mixed
Collector of Sodium Oleate-Tert Dodecyl Mercaptan, Front in Chem, 7.
LIU, Z., 2009. Study on electrochemistry of flotation of lead-antimony-zinc sulfide ore in dithiophosphate systerm. Doctoral
dissertation, 20.
MA, X., HU, Y., ZHONG, H., WANG, S., LIU, G., ZHAO, G., 2016. A novel surfactant S-benzoyl-N,N-
diethyldithiocarbamate synthesis and its flotation performance to galena, Appl. Surf. Sci, 365, 342-345.
ZHAO, L., LIU, W., DUAN, H., WANG, X., FANG, P., LIU, W., ZHOU, X., SHEN, Y., 2021. Design and selection of
flotation collectors for zinc oxide minerals based on bond valence model. Miner. Eng, 160, 106681.
JIA, Y., HUANG, X., HUANG, K., WANG, S., CAO, Z., ZHONG, H., 2019. Synthesis, flotation performance and
adsorption mechanism of 3-(ethylamino)-N-phenyl-3-thioxopropanamide onto galena/sphalerite surfaces, J. Ind. Eng.
Chem., 77, 416-419.
CAO, Z., YANG, Z., ZHANG, C., XIE, L., ZHAO, X., PAN, P., YUAN, Y., QI, W., HE, J., ZHANG, H., XUE, T.,
ZHANG, P., WEI, J., ZHANG, K., ZHAO, J., 2020. Facile synthesis of Sb-Sb2O5@P@C composite and study for the
supercapacitor application, J. Mater. Sci-Mater. El, 31(3), 2406-2409.
ZAKAZNOVA-HERZOG, V.P., HARMER, S. L., NESBITT, H.W., BANCROFT, G.M., FLEMMINGR., PRATT, A.R.,
2006. High resolution XPS study of the large-band-gap semiconductor stibnite (Sb2S3): Structural contributions and
surface reconstruction, Surf. Sci, 600(2), 348-351.
FENG, B., ZHONG, C., ZHANG, L., GUO, Y., WANG, T., HUANG, Z., 2020. Effect of surface oxidation on the
depression of sphalerite by locust bean gum, Miner. Eng, 146.
EJTEMAEI, M., NGUYEN, A.V., 2017. Characterisation of sphalerite and pyrite surfaces activated by copper sulphate,
Miner Eng, 100, 223-232.
HUANG, X., JIA, Y., CAO, Z., WANG, S., ZHONG, H., 2019. Investigation of the interfacial adsorption mechanisms of
2-hydroxyethyl dibutyldithiocarbamate surfactant on galena and sphalerite, Colloids Surf, 583.
PAN, G., SHI, Q., ZHANG, G., HUANG, G., 2020. Selective depression of talc in chalcopyrite flotation by xanthan gum:
Flotation response and adsorption mechanism, Colloids Surf, 600, 29.
LIU, D., ZHANG, G., CHEN, Y., HUANG, G., GAO, Y., 2020. Investigations on the utilization of konjac glucomannan
in the flotation separation of chalcopyrite from pyrite, Miner. Eng, 145.
CAO, Y, SUN, L., GAO, Z., SUN, W., CAO, X., 2020. Activation mechanism of zinc ions in cassiterite flotation with
benzohydroxamic acid as a collector. Miner. Eng, 156,106523.