Separation and Purification Technology 255 (2021) 117732

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Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

Flotation separation performance of malachite from calcite with new

chelating collector and its adsorption mechanism
Zhang Xingrong , Lu Liang , Li Youhui , Zhu Yangge *, Han Long , Li Chengbi
State Key Laboratory of Mineral Processing, BGRIMM Technology Group, Beijing 102600, China

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

Keywords: In this study, the flotation separation performances of malachite from calcite were investigated using a new
Malachite chelating collector S-carboxymethyl-O, O’-dibutyl dithiophosphate (CMDTP) by micro-flotation tests, which
Calcite showed that CMDTP exhibited a stronger collecting power and a better selectivity on malachite than octyl
Flotation separation
hydroxamic acid (OHA), 8-hydroxyquinoline (HQ) and sodium isobutyl xanthate (SIBX). In the flotation sepa­
Chelating collector
Adsorption
ration of artificially mixed minerals, malachite could be separated successfully from calcite at pH around 9.0
when using Na2S as a regulator. Its adsorption mechanism was also studied by FT-IR, zeta potential and XPS
measurements, all of which confirmed that CMDTP showed a better affinity to malachite surface than to calcite
surface. Furthermore, XPS provided obvious evidence that CMDTP could easily react with Cu2+ sites on mala­
chite surface, and only a tiny adsorption occurred on calcite surface without Cu2+ ions.

1. Introduction (NH4)2S is usually used as a sulfidizing reagent to activate malachite,

Malachite is one of the most important copper oxide ores for the
production of copper metal besides copper sulfide ores. In processing
these copper-bearing ores, froth flotation has been proved to be an
effective approach to separate valuable minerals from gangue minerals
[1–5]. As is well known, malachite possesses a good hydrophilic prop­
erty in the pulp due to its abundant hydroxyl groups. Thus, it is very easy
to form a hydrated shell layer on its surface that makes it more hydro­
philic than sulfide copper minerals. As a result, malachite is hard to float
out without any treatment [6,7]. In order to change the floatability of
minerals, a chemical surfactant, known as flotation reagent in froth
flotation, is commonly added into the pulp to change their surface
properties and then to control the hydrophilicity or hydrophobicity of
mineral particles. Therefore, flotation reagent plays a vital role in the
froth flotation [2,8,9], especially in the separation of polymetallic
minerals with similar floatabilities. Nowadays, more and more chal­
lenges exist in mining industry with a rapid consumption of high-grade
and easily-processed ores. Hence, flotation reagent is becoming more
and more important, especially for low-grade and polymetallic re­
fractory ores.
In the flotation of malachite, the most widely used method is to use
xanthate collectors to float malachite minerals in the presence of sul­
fidizing reagents, viz. sulfidization flotation method, in which, Na2S or
and then to promote its recovery [10–12]. Nevertheless, in this method,
the dosage of Na2S or (NH4)2S is usually very large and also easy to
release H2S into the air, which is harmful to the environment and human
beings. In addition, these sulfidizing reagents would decompose rapidly
with processing time in the presence of dissolved oxygen in the pulp
[11,13], thus the shortage of sulfidizing reagents could easily lose their
efficacy and could not activate malachite sufficiently. On the other hand,
an overdose of those reagents would depress malachite in some way.
Therefore, in both the cases, the recovery of malachite will be reduced
[14,15]. Moreover, xanthate collectors used in this method lack excel­
lent selectivity for minerals, which has been proved in practical appli­
cations [10,16,17] and that is unbeneficial to the following separation of
malachite from other co-associated minerals.
To pursue the high flotation efficiency of malachite minerals, several
chelating collectors have been explored and utilized in the froth flota­
tion of malachite, such as oximes [18–20], hydroxamic acids [21–23],
phosphonic acids [24,25], and so on. Although these collectors exhibit
the strong chelating power to malachite, they also lack excellent selec­
tivity against gangue minerals, especially calcium- or iron-containing
minerals [26]. Additionally, it has been found that a handful of het­
erocyclic compounds used for copper sulfide minerals initially, such as
2-mercaptobenzothiazole (MBT), 2-mercaptobenzimidazole (MBI) and
2-mercaptobenzoxazole (MBO), could be applied in collecting malachite

* Corresponding author.
E-mail address: zhuyangge@126.com (Z. Yangge).

https://doi.org/10.1016/j.seppur.2020.117732
Received 14 March 2020; Received in revised form 7 September 2020; Accepted 9 September 2020
Available online 17 September 2020
1383-5866/© 2020 Elsevier B.V. All rights reserved.
Z. Xingrong et al.
as well [6,27–29]. However, these collectors also have their own
shortcomings, for instance, poor hydrophobicity, low synthesis yields,
high cost or environmental pollution problems [30,31]. In order to
overcome these deficiencies, Liu and his group have designed and syn­
thesized a series of azole-thione heterocyclic compounds using as mal­
achite collectors [32–35], for example, HATT and HpTT, in which, Cu-S
and Cu-N bonds were formed via S, N-donor atoms [32,35,36]. In spite
of excellent selectivity of these new compounds on malachite against
calcite, which is a common gangue mineral in malachite flotation, they
haven’t been applied in industry due to their low yields (about 80.0%)
[32,33] and high cost.
In previous work [37,38], dithiophosphate collector was used to
collect copper oxide minerals, such as cuprite and malachite, and they
exhibited good affinity to oxide copper minerals. However, its recovery
was not satisfying. In order to improve its collecting power, in this
research, a new chelating collector, S-carboxymethyl-O, O’-dibutyl
dithiophosphate (CMDTP) containing P, S and O atoms, was introduced
as a malachite collector to separate it from calcite, a calcium-containing
gangue mineral. The flotation performances of malachite and calcite
were investigated under different experiment conditions in the presence
of CMDTP. Furthermore, FT-IR, zeta potential and XPS measurements
were employed to explore the adsorption mechanism of CMDTP on
mineral surfaces. All these findings would be helpful for us to under­
stand how to separate malachite from calcium-bearing gangue minerals
with CMDTP in the following works and would be beneficial to promote
the recovery and the separation efficiency of malachite minerals.
2. Materials and methods
2.1. Mineral samples and reagents
Malachite and calcite samples used in present study were originated
from Hubei Province and Hunan Province, China, respectively. Both
these two samples were crushed and handpicked to obtain high purity
minerals, and then dry ground in a ceramic ball mill, separately. After
that, the ground samples were dry-sieved to gather the size fractions
between 38 μm and 74 μm, which were used in the following micro-
flotation tests. Those samples with particle size less than 5 μm were
collected to conduct FT-IR, zeta potential and X-ray photoelectron
spectra (XPS) experiments. The purities of malachite and calcite could
reach 97.6% and 98.4%, individually, based on X-ray diffraction (XRD)
analysis and chemical analysis as shown in Fig. 1 and Table 1.
CMDTP with a purity of more than 98.0% was synthesized in our lab
[39] and used as the malachite collector, compared with three tradi­
tional collectors, viz. octyl hydroxamic acid (OHA), 8-hydroxyquinoline
(HQ) and sodium isobutyl xanthate (SIBX), which were provided by
Fig. 1. XRD of (a) malachite and (b) calcite minerals.
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Separation and Purification Technology 255 (2021) 117732
commercial suppliers. NaOH and HCl solutions with appropriate con­
centrations were used to adjust the pulp pH values. For the artificially
mixed minerals micro-flotation tests, Na2S with a chemical grade was
chosen as a regulator. Besides, distilled water was used throughout the
whole study and all other chemicals were of analytical reagent grades
and obtained from Sinopharm Chemical Reagent Co., Ltd, China.
2.2. Experimental methods
2.2.1. Micro-flotation tests
Micro-flotation tests were divided into two groups, including the
single mineral micro-flotation tests and the artificially mixed minerals
micro-flotation tests. All the micro-flotation tests were carried out by a
XFG-76 flotation machine with a 40-mL plexiglass cell. In each test, the
agitation speed was controlled at 1754 rpm.
In a single mineral micro-flotation test, 2.0 g of malachite or calcite
samples as mentioned in Section 2.1 were placed into a 50-mL beaker,
and then 30 mL distilled water was added. Later, the beaker containing
these samples was put in an ultrasonic bath for 3 min to clean the
mineral surface. After that, the upper clear liquid was removed, and then
the remaining mineral samples were transferred into the flotation cell
with total 30 mL distilled water. The pulp pH was regulated to a desired
value by NaOH or HCl solutions. 2 min later, the collector was intro­
duced into the flotation cell and also the frother or the regulator was
added if necessary for another 2 min stirring. Finally, the micro-flotation
test was conducted for 4 min. The froth products and the tailings were
gathered, dried and weighed, respectively. The flotation recovery for
each test was calculated according to Eq. (1).
For an artificially mixed minerals micro-flotation test, 2.0 g of mixed
minerals with a 1/1 mass ratio of malachite to calcite were used as the
feed samples. All the procedures were kept the same as the single min­
eral micro-flotation test as above. The flotation recovery for malachite
or calcite in each test was calculated based on Eq. (2), respectively.
mf
εpm = × 100% (1)
mf + mt
mf × β1
εM/C = × 100% (2)
mf × β1 + mt × β2
where εpm is the recovery of the pure malachite or calcite minerals, mf
(g) and mt (g) are the mass of the froth products and the tailings,
separately. εM/C expresses the recovery of malachite or calcite in froth
products. β1 (w%) is the grade of Cu or Ca in the froth products and β2 (w
%) represents the grade of Cu or Ca in the tailings. Herein, each test was
conducted for three times, and each calculated recovery presented here,
according to Eqs. (1) and (2), was an average value of these three
Z. Xingrong et al.
Table 1
Chemical analysis of pure malachite and calcite minerals (wt%).
Minerals Cu Ca Mg SiO2
Malachite 56.53 4.49 0.03 0.50
Calcite 0.03 39.61 0.29 0.33
independent flotation tests with an error less than ±3.0%.
2.2.2. FT-IR spectra detections
A Nicolet 740 Fourier transform infrared (FT-IR) spectrometer (USA)
was used to characterize FT-IR spectra of CMDTP collector, malachite
and calcite samples untreated and treated by CMDTP, and calcite sam­
ples treated by CMDTP in the presence of Cu2+ ions.
Untreated malachite and calcite samples with particle size less than
5 μm were directly used for FT-IR detection. Those treated samples by
CMDTP were prepared as following steps: 0.5 g of above untreated
samples were placed into a 250 mL conical flask, and then 90.0 mL
distilled water was added. At pH around 9.0, 10.0 mL CMDTP solutions
with a concentration of 1.0 × 10− 3 mol/L in ethanol were introduced
into the conical flask with 2 h stirring at room temperature. Besides,
when preparing calcite samples treated by CMDTP in the presence of
Cu2+ ions, 3.0 mL CuSO4 solutions with a concentration of 1.0 × 10− 4
mol/L in water was firstly added into the conical flask before CMDTP.
After that, the samples were filtered and washed thrice with distilled
water, and then dried in a vacuum desiccator under vacuum at 50 ℃ for
one week. Ultimately, those treated samples were used for FT-IR
detection.
2.2.3. Zeta potential measurements
A NANO-ZS90 zeta potential analyzer (Malvern Instruments Ltd.
Britain) was applied to measure zeta potentials of malachite and calcite
samples with and without CMDTP treatment. 50 mg of pure malachite or
calcite minerals with particle size less than 5 μm were introduced into a
100 mL beaker, and then 50.0 mL 1.0 × 10− 3 mol/L KCl solutions with
or without 1.0 × 10− 4 mol/L CMDTP were added. Thereafter, the pulp
pH was regulated to an expected value with dilute HCl or NaOH solu­
tions. With a 5 min stirring, the zeta potentials of the suspensions at
different pH values with or without CMDTP were determined in KCl
solutions as a supporting electrolyte. On the other hand, in order to
detect the influence of Cu2+ ions on calcite, 2.0 mL 1.0 × 10− 4 mol/L
CuSO4 in KCl solutions were added into the suspension to repeat above
measurements. Each presented zeta potential was an average value of
ten individual tests with a deviation of ± 5 mV.
2.2.4. XPS detections
An ESCALAB 250XI spectrometer (Thermo Scientific, USA) with
monochromatic Al Kα radiation as an excitation source (hv = 1486.6 eV)
was employed to perform X-ray Photoelectron Spectroscopy (XPS) of
untreated or treated malachite and calcite mineral samples. The mea­
surements were operated in an analytical chamber with a high vacuum
of less than 1.0 × 10− 9 Torr. The wide survey spectra were recorded
from 0 eV to 1200 eV with a pass energy of 100 eV and a step size of 1 eV
for at least three scans. Herein, a binding energy (B.E.) at 284.6 eV
assigned to C 1s was applied to calibrate the spectrometer.
The method for preparing malachite and calcite samples was the
same as that described in Section 2.3.
3. Results and discussion
3.1. Micro-flotation tests results for single minerals
In this section, the influences of the CMDTP dosage and the pulp pH
on the flotation performances of malachite and calcite were investigated
by micro-flotation tests. Meanwhile, its flotation efficiency on malachite
with other three traditional collectors, viz. OHA, HQ and SIBX, was
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Separation and Purification Technology 255 (2021) 117732
Al Fe Mn P C
0.06 0.22 0.03 0.23 5.30
0.03 0.05 0.03 – 11.82
compared. All the results are shown in Figs. 2-4.
As observed in Fig. 2, CMDTP dosage has a great influence on the
flotation recovery of malachite and only a slight influence on that of
calcite. This phenomenon indicates that CMDTP exhibits a better
selectivity on malachite than on calcite. The flotation results also
demonstrate that an optimal dosage of CMDTP for malachite is around
1.0 × 10− 4 mol/L, at which, the recovery of malachite could reach over
78.0%, while the recovery of calcite is only about 15.0%.
The flotation performances of malachite and calcite as a function of
pH with 1.0 × 10− 4 mol/L CMDTP as the collector were displayed in
Fig. 3, in which, it is clear that the recovery of malachite decreases
sharply when the pulp pH is greater than 9.0, while within pH 6.0–9.0,
malachite could float out with a good flotation recovery of more than
70.0%. Nevertheless, calcite is not sensitive to the pulp pH within a
whole pH range of 6.0–12.0. Although its flotation recovery expresses a
slowly increasing tendency, it is still kept at around 15.0%. These
flotation results indicate that calcite is hardly floated out with CMDTP
collector within a pH range of 6.0–12.0.
As displayed in Fig. 4, when using SIBX as the collector with no Na2S
activator, SIBX cannot collect malachite effectively, which shows a good
accordance with previous research [40]. When 2.0 × 10− 4 mol/L Na2S is
added together with SIBX, the recovery of malachite is obviously pro­
moted, however, its recovery can only reach around 55.0% with 3.0 ×
10− 4 mol/L SIBX. Otherwise, HQ and OHA exhibit the better flotation
performances for malachite than SIBX with Na2S as an activator, but less
than CMDTP. At the same dosage of 1.0 × 10− 4 mol/L, the recovery of
malachite with CMDTP is almost 78.0%, a rise of 40.0% greater than
other three collectors, which infers that CMDTP exhibits a superior
flotation performance on malachite in comparison with OHA, HQ and
SIBX.
As reported in a previous research [41], malachite could release
Cu2+ ions into the pulp. Therefore, when mixed with calcite gangue
mineral, the released Cu2+ ions by malachite might promote the flota­
tion behavior of calcite and then to lower the separation efficiency of
malachite from calcite. Based on this consideration, we investigated the
effects of Cu2+ ions on the recoveries of malachite and calcite with
Fig. 2. The influences of CMDTP dosage on the flotation performances of
malachite and calcite without frother at pH around 7.5.
Z. Xingrong et al.
Fig. 3. The flotation performances of malachite and calcite as a function of pH
in the presence of 1.0 × 10− 4 mol/L CMDTP.
Fig. 4. The flotation performances of malachite with CMDTP, OHA, HQ and
SIBX at initial pH 7.5.
different CMDTP dosages. The flotation results are listed in Fig. 5, in
which, the concentration of Cu2+ ions was 0.18 mg/L (equal to around
2.8 × 10− 6 mol/L), as we measured in the pulp of the artificially mixed
minerals with a 1:1 mass ratio of malachite to calcite.
It is clear that Fig. 5 provides enough evidence that Cu2+ ions have a
positive effect on the flotation behavior of calcite as we speculated, but
have a slight influence on malachite. That is Cu2+ ions could really in­
crease the recoveries of calcite as observed in Fig. 5. This interesting
phenomenon should be considered in the following flotation separation
tests for artificially mixed minerals.
3.2. Micro-flotation separation results for artificially mixed minerals
It is known from above micro-flotation results for single minerals,
CMDTP exhibits a stronger affinity and a superior selectivity on mala­
chite than calcite, and CMDTP might be regarded as a potential collector
to separate malachite from calcite gangue mineral. Therefore, we
designed an experiment for the flotation separation of artificially mixed
minerals with a malachite to calcite mass ratio of 1 to 1, and investigated
its separation efficiency with various CMDTP dosages, as shown in
Fig. 6.
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Separation and Purification Technology 255 (2021) 117732
Fig. 5. The effects of Cu2+ ions on the flotation performances of malachite and
calcite at pH around 7.5 with various CMDTP dosages.
It is clear that the recoveries of malachite and calcite in froth prod­
ucts show an obvious upward tendency with increasing CMDTP dosage.
When the CMDTP dosage is up to 1.0 × 10− 4 mol/L, more than 80.0% of
malachite and calcite minerals are floated into the froth products, which
indicates that malachite isn’t separated successfully from calcite. This is
in contradiction with the micro-flotation results for single minerals as
described in Figs. 2–4. Conversely, this phenomenon indirectly proves
that Cu2+ ions released by malachite indeed promote the floatability of
calcite when mixing these two minerals as mentioned in Fig. 5.
In order to eliminate the effect of Cu2+ ions released by malachite,
we introduced Na2S as the regulator with a dosage of 2.0 × 10− 4 mol/L
to explore the separation efficiency with various CMDTP dosages. The
comparison results are also displayed in Fig. 6. As observed in Fig. 6, in
the presence of Na2S, the calcite recovery in the froth products is kept at
only around 10.0%. However, the malachite recovery is not very high at
a low CMDTP dosage. Clearly, increasing CMDTP dosage is beneficial to
promote the malachite recovery and has a no significant influence on the
calcite recovery in the froth products. When the CMDTP dosage is up to
2.0 × 10− 4 mol/L, the malachite recovery could achieve almost 80.0%,
with a calcite recovery of less than 8.0%. At this point, the flotation
separation of malachite from calcite is achieved successfully.
Fig. 6. Flotation separation results of artificially mixed minerals samples with
various CMDTP dosages in the presence and absence of Na2S regulator at initial
pH 7.5.
Z. Xingrong et al.
As illustrated in Fig. 6, Na2S was beneficial to the flotation separation
of malachite from artificially mixed minerals. Herein, we studied the
effect of Na2S dosage on the flotation separation efficiency of artificially
mixed minerals when the dosage of CMDTP is 2.0 × 10− 4 mol/L and the
pulp initial pH is 9.0. The flotation separation results are listed in Fig. 7.
It can be seen in Fig. 7, Na2S dosage has a significant influence on the
calcite recovery in the malachite concentrate (the froth products), while
has only a slight influence on malachite recovery. The calcite recovery in
the malachite concentrate is decreasing with increasing Na2S dosage.
When Na2S dosage is up to 2.0 × 10− 4 mol/L, over 75.0% of malachite
could be separated against calcite, while the calcite recovery is reduced
to around 12.0%. These experiment results confirm that the usage of
Na2S is favorable to separate malachite from calcite. Therefore, a Na2S
dosage of 2.0 × 10− 4 mol/L is selected as the optimum value in present
study.
As illustrated in Fig. 8, calcite exhibits different flotation behaviors
when mixed with malachite in the presence of Na2S from those in the
single mineral micro-flotation tests compared with micro-flotation tests
in Fig. 3. That is the calcite recovery in froth products goes down from
almost 78.0% to less than 5.0% with the increase of pH, while in the
single mineral micro-flotation tests, calcite is not sensitive to pH as
shown in Fig. 3. For malachite, in both the cases, malachite shows
almost the same flotation behaviors within pH 6.0–12.0. When the pH is
greater than 9.0, the malachite recovery in froth products drops sharply.
It can be learnt from Fig. 8 that the optimum pH for the separation of
malachite against calcite is around 9.0 in the presence of Na2S using
CMDTP as the collector.
3.3. FT-IR spectra analysis
In order to explore the adsorption mechanism of CMDTP on mala­
chite and calcite surface, we investigated FT-IR spectra of treated and
untreated malachite or calcite as presented in Fig. 9. In the spectra of
calcite, the peaks at around 2980 cm− 1, 2865 cm− 1, 2510 cm− 1, 1792
cm− 1, 1450 cm− 1, 860 cm− 1 and 704 cm− 1 are assigned to the charac­
teristic adsorption peaks of calcite, appearing in Fig. 9(a–c), which
agrees well with the results reported in previous literatures [42,43].
When treated by CMDTP in the presence or absence of Cu2+ ions, the
peaks at around 1765 cm− 1 and 585 cm− 1 are found in both of Fig. 9(b)
and (c), which are attributed to the stretching vibration of C=O group
and the symmetrical stretching vibration of PS2 [44] from CMDTP.
Besides, the peak at around 2903 cm− 1 in Fig. 9(c) belonging to CMDTP
Fig. 7. The effect of Na2S dosage on the flotation separation efficiency of
artificially mixed minerals under conditions of 2.0 × 10− 4 mol/L CMDTP and
the pulp initial pH 9.0.
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Separation and Purification Technology 255 (2021) 117732
Fig. 8. The influence of pH on the flotation separation results of artificially
mixed minerals (CMTDP: 2.0 × 10− 4 mol/L, Na2S: 2.0 × 10− 4 mol/L).
is more obvious than that in Fig. 9(b). However, the adsorption peak of
saturated C-H stretching vibrations at around 2960 cm− 1 is not found in
both Fig. 9(b) and (c), which is probably caused by the covering of the
wide and strong peaks of CO2– 3 . All these evidence prove that CMDTP
could adsorb on calcite surface in the presence or absence of Cu2+ ions.
However, their adsorption strength are different, which can be testified
by following XPS analysis.
Fig. 9(d) shows the FT-IR spectrum of malachite, which keeps a good
accordance with the previous research [26]. After treated by CMDTP, a
peak at 2961 cm− 1 assigned to the saturated C-H stretching vibration
appears in the spectrum of malachite as shown in Fig. 9(e), which infers
that CMDTP has adsorbed onto malachite surface.
3.4. Zeta potential analysis
Fig. 10 shows the zeta potential curves of malachite and calcite with
or without 1.0 × 10− 4 mol/L CMDTP as a function of pH. As seen in
Fig. 10, the zeta potential curve of malachite is similar to that reported
in the previous work [36,38,45] and its isoelectric point (IEP) appears at
pH around 8.2, which is very close to the reported pH value. When
CMDTP collector is added, an obvious negative shift occurs within pH
5.0–10.0. Simultaneously, the IEP of malachite moves to a pH around
6.3. These changes indicate that CMDTP has adsorbed onto malachite
surface within pH 5.0–10.0. Moreover, a similar zeta potential curve of
calcite is also found in Fig. 10 as those presented in previous literatures
[46,47]. Interestingly, there is no apparent shifts happening for calcite
before and after CMDTP addition. This phenomenon implies a very tiny
adsorption of CMDTP on calcite surface. While Cu2+ ions are added into
the calcite suspension, its zeta potential moves obviously to a positive
value as observed in Fig. 10, which indicates that Cu2+ ions could adsorb
onto calcite surface and activate its floatability as we speculated before,
giving a good explanation for the micro-flotation tests results as pre­
sented in Fig. 5.
3.5. XPS analysis
The survey XPS spectra of malachite with and without treatment of
CMDTP are listed in Fig. 11. By comparing these two XPS spectra, it is
drawn that two new peaks at around 163.5 eV and 133.6 eV appear in
the spectrum of malachite after treatment by CMDTP, which are
attributed to the S 2p and P 2p in the CMDTP structure, individually
[26,48]. It can be inferred that CMDTP has adsorbed onto malachite
surface apparently.
The survey XPS spectra of calcite, calcite with CMDTP or Cu2+ ions
and calcite with Cu2+ ions and CMDTP are presented in Fig. 12.
Z. Xingrong et al. Separation and Purification Technology 255 (2021) 117732

Fig. 9. FT-IR spectra of (a) calcite, (b) calcite with CMDTP, (c) calcite with Cu2+ ions and CMDTP, (d) malachite untreated and (e) malachite treated by CMDTP.

It is clear that there are no evident changes in XPS spectra of calcite

before and after CMDTP adsorption in the absence of Cu2+ ions as seen
in Fig. 12(a) and (b). When Cu2+ ions are added, a characteristic peak
assigned to Cu 2p appears in the XPS spectrum of calcite. Furthermore,
when CMDTP is added together with Cu2+ ions, the peak of Cu 2p is also
found in its XPS spectrum as well as the peaks of S 2p and P 2p belonging
to CMDTP collector, as illustrated in Fig. 12(c) and (d).
The high-resolution XPS spectra of Cu 2p, S 2p and P 2p of untreated
and treated calcite by Cu2+ ions or CMDTP are displayed in Fig. 13(1)–
(3). The characteristic peak parameters of Cu 2p XPS are listed in
Table 2.
As observed in Fig. 13, several changes have been found in the high-
resolution XPS of Cu 2p, S 2p and P 2p before and after treatment of
calcite. However, when only treated by CMDTP, no obvious changes are
discovered in the XPS of S 2p and P 2p assigned to CMDTP, which
demonstrates that CMDTP is difficult to adsorb onto calcite surface and
can’t float it out. This conclusion has been proved by the micro-flotation
results as shown in Fig. 2. In the presence of only Cu2+ ions, the peak at
934.75 eV (as shown in Table 2) assigned to Cu 2p [26,49] appears in the
4
XPS spectrum. That is to say Cu2+ ions has adsorbed on calcite surface,
Fig. 10. The zeta potential of malachite and calcite with or without 1.0 × 10−
which agrees well with the zeta potential analysis in Fig. 10. When
mol/L CMDTP.
CMDTP is introduced after Cu2+ ions, the peak of Cu 2p remains in the
XPS spectrum as shown in Fig. 13(1-d). Simultaneously, the peaks of S

Fig. 11. The survey XPS spectra of malachite (a) before and (b) after treatment
by CMDTP.
Fig. 12. The survey XPS spectra of (a) calcite, (b) calcite with CMDTP, (c)
calcite with Cu2+ ions and (d) calcite with Cu2+ ions and CMDTP.

6
Z. Xingrong et al. Separation and Purification Technology 255 (2021) 117732

Fig. 13. High-resolution XPS of (1) Cu 2p, (2) S 2p and (3) P 2p of (a) calcite, (b) calcite with CMDTP, (c) calcite with Cu2+ ions and (d) calcite with Cu2+ ions
and CMDTP.

are added, the atomic concentration of Cu goes up sharply from 0.18 to

Table 2
11.70, while the atomic concentration of Ca reduces from 17.07 to 9.14,
The characteristic parameters of Cu 2p XPS.
suggesting Cu2+ ions have adsorbed on calcite surface. When CMDTP is
Malachite Calcite added after Cu2+ ions, it is found that the atomic concentration of Cu
Untreated Treated by CMDTP Treated Treated by Cu2+ increases to 13.79 and Ca decreases to 4.99, meanwhile, the atomic
by Cu2+ and CMDTP concentrations of S and P increase to 5.40 and 2.46 on their surfaces. The
Cu B.E./eV 934.85 932.75 934.40 934.75 932.80 934.65 ratio of S to P is 2.19, which is very close to 2.0, keeping a good
Assignment Cu-O Cu- Cu-O Cu-O Cu- Cu-O accordance with the formula of CMDTP [39]. This phenomenon dem­
CMDTP CMDTP onstrates that Cu2+ ions could adsorb on calcite surface to promote its
interactions with CMDTP and then to activate its floatability. As a result,
2p at 163.5 eV and P 2p at 133.6 eV [26,48] are also found in the XPS the flotation recovery of calcite increases in the presence of Cu2+ ions
spectrum of treated calcite by Cu2+ ions and CMDTP. This phenomenon and CMDTP. The same conclusion could be drawn from Fig. 5.
indicates that Cu2+ ions already adsorbed on calcite surface could pro­ Based on above analysis, we propose a flotation separation model of
mote the adsorption of CMDTP on calcite surface and then to improve its malachite from calcite when using CMDTP collector as shown in Fig. 14.
flotation recovery as displayed in Fig. 5. For single minerals, CMDTP is very easy to adsorb onto malachite sur­
Besides, as shown in Table 2, the Cu 2p XPS band emerged at 934.8 face. When mixed with calcite gangue minerals, Cu2+ ions released by
eV, which could be attributed to Cu-O species from untreated malachite malachite could preferentially adsorb onto calcite surface. At this time,
and treated calcite by Cu2+ ions. After adsorption of CMDTP, the Cu 2p if CMDTP is added, Cu2+ ions already adsorbed on calcite surface would
XPS is divided into two characteristic bands. One locates at 932.8 eV promote the adsorption of CMDTP and then to improve its floatability,
assigned to Cu-CMDTP complex, and the other locates at 934.5 eV which results in a poor separation efficiency. However, when Na2S is
originated from bulk-phase Cu2+ of malachite and already adsorbed added before CMDTP, Na2S could remove Cu2+ ions on calcite surface
Cu2+ on calcite surface, inferring the generation of the surface Cu- and then to eliminate its negative effect. Finally, malachite is separated
CMDTP complexes on malachite surface and calcite surface treated by successfully against calcite mineral.
Cu2+ ions [40].
Table 3 lists the results of atomic concentrations of elements of 4. Conclusions
malachite and calcite before and after treatment, including Cu 2p, Ca 2p,
C 1s, O 1s, S 2p and P 2p. The results indicate that the atomic concen­ In present research, the flotation performances of malachite and
trations of S and P increase on all minerals surfaces when treated only by calcite were investigated when using S-carboxymethyl-O, O’-dibutyl
CMDTP. Apparently, the atomic concentrations of S and P on malachite dithiophosphate (CMDTP) as a new chelating collector. Its separation
are greater than those on calcite surface, inferring that CMDTP has a mechanism was explored and evaluated by using FT-IR, zeta potential
stronger adsorption on malachite surface. For calcite, when Cu2+ ions and XPS measurements.
Micro-flotation findings demonstrated that CMDTP exhibited a
stronger adsorption and a better selectivity on malachite than octyl
Table 3 hydroxamic acid (OHA), 8-hydroxyquinoline (HQ) and sodium isobutyl
Atomic concentrations of elements of malachite and calcite before and after xanthate (SIBX). In the flotation separation of malachite from calcite, an
treatment. efficient flotation separation could be realized at pH around 9.0 when
Species Atomic Concentration /% using Na2S as a regulator.
FT-IR spectra suggested that CMDTP could adsorb on malachite and
Cu 2p Ca 2p C 1s O 1s S 2p P 2p
calcite surface. Zeta potential results illustrated that CMDTP possessed a
Malachite 23.45 22.74 51.17 0.76 1.89
–
better affinity to malachite than calcite. Cu2+ ions could adsorb onto
Malachite with CMDTP 19.29 – 28.31 45.92 3.59 2.89
Calcite 0.18 17.07 26.19 56.08 0.25 0.23 calcite surface and then to activate calcite. XPS further proved that
Calcite with CMDTP 0.20 16.56 27.37 54.87 0.56 0.44 CMDTP had a stronger adsorption on malachite surface than on calcite
Calcite with Cu2+ ions 11.70 9.14 24.97 51.10 2.05 1.04 surface. In the presence of Cu2+ ions, the interaction between CMDTP
Calcite with Cu2+ ions and 13.79 4.99 26.77 46.60 5.40 2.46 and calcite would be strengthened. So, when using CMDTP as a collector
CMDTP
to separate malachite from calcite, Na2S was usually added to eliminate

7
Z. Xingrong et al.
Fig. 14. The suggested flotation separation model of malachite from calcite.
the negative effect of Cu2+ ions released by malachite.
CRediT authorship contribution statement
Zhang Xingrong: Conceptualization, Methodology, Software,
Writing - original draft. Lu Liang: Investigation, Software, Data cura­
tion, Visualization. Li Youhui: Investigation, Resources, Data curation.
Zhu Yangge: Methodology, Validation, Supervision. Han Long: Su­
pervision, Project administration. Li Chengbi: Methodology,
Validation.
Declaration of Competing Interest
The author declare that there is no conflict of interest.
Acknowledgements
The authors would gratefully thank for the financial supports pro­
vided by the National Natural Science Foundation of China (Grant No.
51974030 and 51634009), the National Key R&D Program of China
(Grant No. 2018YFE0121000 and 2017YFE0133100), the International
S&T Cooperation Program of China (ISTCP) (Grant No. 2015DFA60330)
and the BGRIMM fund program in this research.
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