Minerals Engineering 137 (2019) 118–123

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Investigation on flotation separation of chalcopyrite from arsenopyrite with T

a novel collector: N-Butoxycarbonyl-O-Isobutyl Thiocarbamate
⁎ ⁎
Jiwei Lu, Zhongyun Tong , Zhitao Yuan , Lixia Li
School of Resources and Civil Engineering, Northeastern University, Shenyang 110819, China

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

Keywords: The efficient separation of chalcopyrite from arsenic-bearing minerals, especially arsenopyrite, remains a
Chalcopyrite challenge in practice. In this work, a novel reagent of N-Butoxycarbonyl-O-Isobutyl Thiocarbamate (NBOIT) was
Arsenopyrite employed in both single and mixed binary mineral flotation, and it proved to be highly effective for the flotation
Flotation separation. Furthermore, the role of the pH and NBOIT concentration was evaluated. Additionally, the me-
Selective adsorption
chanism of the selective separation was investigated systemically via zeta potential measurements, Fourier
XPS
transform infrared (FTIR) analysis and X-ray photoelectron spectroscopy (XPS) analysis. It turns out that the
selective chemisorption of NBOIT on chalcopyrite (in the form of Cu-NBOIT complex) over arsenopyrite is as-
cribed to its the stronger reactivity and the high density of Cu ions on the chalcopyrite surfaces. The XPS analysis
results also confirmed the generation of a Cu-NBOIT complex on the surface of chalcopyrite.

1. Introduction magnesia mixture as a selective depressant to separate arsenopyrite

Arsenic is one of the most dangerous inorganic pollutants, causing
environmental and health emergencies in several areas of the world
(Lattanzi et al., 2008). It is a penalty element in many base metal
concentrates that are destined for smelting to produce the relevant
metallic products. It is of economic and environmental interest to re-
move arsenic minerals at an early stage of processing such as flotation.
Unfortunately, arsenic minerals generally have similar flotation beha-
vior to the valuable minerals with which they are associated. Arseno-
pyrite (FeAsS), which may associate with chalcopyrite, usually reports
to the copper concentrate in conventional flotation due to its similar
flotation properties. Arsenic, in the chalcopyrite concentrate, causes
environmental problems and also problems in the subsequent pyr-
ometallurgical process (Guo and Yen, 2005; Fornasiero et al., 2001;
Tayebi-Khorami et al., 2017). In industry it has been shown that ar-
senopyrite is difficult to remove from copper concentrate by conven-
tional flotation techniques.
Arsenic removal in sulphide flotation has been studied extensively
with various approaches (Ma and Bruckard, 2009). A range of arsenic
minerals including arsenopyrite, tetrahedrite, tennantite and enargite
occurs in various copper deposits in the world (Plackowski et al., 2012).
Abeidu and Almahdy (1980) found that a magnesia mixture forms a
strongly hydrophilic layer on arsenopyrite surfaces which inhibits the
adsorption of xanthates on arsenopyrite. Matis et al. (1992) used a
from a bulk auriferous pyrite concentrate from the Olympias plant in
Chalkidi. Chen et al. (2001) found that thioglycolic acid (TGA), an
organic depressant that is known to depress chalcopyrite in sulphide
flotation, does not affect the flotation of arsenopyrite. Chanturiya et al.
(2000) reported that dimethyldithiocarbamate, a coagulant in the flo-
tation of nonferrous metal ores, significantly depresses arsenopyrite at
pH 10.3 while chalcopyrite is only affected very weakly. Sirkeci (2000)
reported similar phenomenon using hexyl thioethylamine as a collector
in a single mineral study and attributed the differential flotation to the
higher adsorption rate of hexyl thioethylamine on to chalcopyrite in
comparison to arsenopyrite. From a large number of investigations in
this field, the selective flotation reagents were found to play an im-
portant role in the collection process.
Alkoxycarbonyl thiocarbamate, which can be made from butyl
chloroformate, sodium thiocyanate and isobutanol, has good selectivity
for copper, its collecting ability is stronger than Z-200, and its toxicity
and its potential for pollution are lower than for xanthate, while its use
under low alkaline conditions can effectively lower the amount of lime
used. It can thereby reduce costs and protect the environment of the
mine, while low alkaline conditions are conducive to the recovery of
rare metals and more efficient use of mineral resources. Many sulfide
ore flotation plants use it instead of xanthate. (Han et al., 2001; Yang
and Liu, 2015; Yuan et al., 2007; Zhang et al., 2008). The strong
electron-withdrawing ethoxycorbany group adjacent to C]S group

⁎
Corresponding authors.
E-mail addresses: tzhongyun@yeah.net (Z. Tong), yuanzhitao@mail.neu.edu.cn (Z. Yuan).

https://doi.org/10.1016/j.mineng.2019.04.003
Received 29 October 2018; Received in revised form 1 April 2019; Accepted 1 April 2019
0892-6875/ © 2019 Elsevier Ltd. All rights reserved.
J. Lu, et al.
Table 1
Chemical compositions of chalcopyrite and arsenopyrite.
Elements Fe S Cu As SiO2 MgO Al2O3
Chalcopyrite 30.4 35.9 33.2 0.1 0.1 0.2 0.1
Arsenopyrite 34.1 18.7 0.2 45.7 0.7 – 0.5
decreases the electron density of the sulfur in N-Butoxycarbonyl-O-
Isobutyl Thiocarbamate, which improves NBOIT’s selectivity against
arsenic minerals (Liu et al., 2006). In this study, N-Butoxycarbonyl-O-
Isobutyl Thiocarbamate was employed as a collector to make full use of
its two advantages, i.e., a high selectivity and intense collecting ability,
respectively. The flotation performance and selectively of NBOIT on
chalcopyrite were evaluated by flotation experiments, and the adsorp-
tion mechanism of NBOIT on the mineral surface was also examined by
zeta potential measurements, Fourier transform infrared (FTIR) spec-
troscopy analysis, and X-ray photoelectron spectroscopy (XPS) analysis.
2. Materials and methods
2.1. Minerals and reagents
Both chalcopyrite and arsenopyrite samples were obtained from the
Inner Mongolia Autonomous Region of China. The hand-picked mineral
samples were crushed and then ground in a porcelain ball mill. Then
the −75 + 38 μm size fraction was obtained by wet-sieving for flota-
tion testing. As shown in Table 1 and Fig. 1, the results of element
analysis and X-ray diffraction spectra (XRD) of samples indicated that
the purity of the samples of chalcopyrite and arsenopyrite was 96.4%
and 98.3%, respectively, which met the purity requirement for the
study. Artificial mixed mineral was prepared by mixing chalcopyrite
and arsenopyrite samples at a mass ratio of 1:1.
The N-Butoxycarbonyl-O-Isobutyl Thiocarbamate (NBOIT) was in-
dustry grade. Its purity was greater than 85% and its chemical formula
is CH3CH(CH3)CH2eOe(C]S)eNHe(C]O)eOeC4H9. Other chemi-
cals were of AR grade. Sulfuric acid (H2SO4) and sodium hydroxide
(NaOH) were used as pH regulators. Deionized water was used
throughout all experiments.
2.2. Flotation tests
Flotation of single minerals and separation of artificial mixed sam-
ples (chalcopyrite and arsenopyrite at a mass ratio 1:1) were carried out
in a XFG mechanical flotation machine with a 40 mL flotation cell. Tests
with both single and mixed minerals employed a sample mass of 2 g.
Fig. 1. X-ray diffraction patterns of chalcopyrite (a) and arsenopyrite (b).
Minerals Engineering 137 (2019) 118–123
The mineral samples were mixed with 40 mL deionized water and
conditioned for 2 min at a speed of 1920 r/min while the desired pH
CaO value was adjusted using H2SO4 or NaOH. Lime and NBOIT were added
into the cell one after another with a 3 min conditioning time and fol-
– lowed by flotation for 5 min. The froth products and tailings were
0.1
collected, filtered, and dried. The recovery was calculated based on
weight and elemental contents of the products obtained.
2.3. Zeta potential measurement
The zeta potential values of minerals before and after interacting
with collector were measured by a zeta plus meter (Nano-ZS90 Zeta
plus, Malvern Instruments Ltd., UK). 20 mg of −10 μm mineral was
added to 50 mL of 10−3 mol/L potassium nitrate solution as a sup-
porting electrolyte and mechanically stirred for 10 min and the pH was
adjusted to each required value in the range of 3–11 using H2SO4 or
NaOH. In each case, the zeta potentials were measured and the average
of three independent measurements was accredited.
2.4. FTIR spectra analysis
The Fourier transform infrared (FTIR) spectra were recorded at a
4 cm−1 resolution in the 4000–400 cm−1 region through KBr disks by a
Nicolet 380 FTIR spectrometer at room temperature. 1 g of −10 μm
samples was added into 30 mL deionized water with or without NBOIT
at the desired pH values and conditioned for 30 min. Afterwards,
samples were filtered, purged with deionized water and dried at 35 °C.
Approximately 2 mg of the sample was thoroughly mixed with 200 mg
of spectroscopic grade KBr as diluent and then pressed into pellets for
FTIR measurements.
2.5. XPS analysis
XPS spectra were recorded using an American Thermo ESCALAB
250 XI spectrometer using Al Kα X-rays (1486.6 eV) as the sputtering
source at a power of 150 W (15 Kv × 10 Ma). The XPS measurements
were performed inside the analysis chamber operating in a high va-
cuum of 5.0 × 10−7 Pa. A value of 284.7 eV was adopted as the stan-
dard C (1s) to calibrate binding energy.
3. Results and discussion
3.1. Flotation of single minerals
The flotation behaviors of chalcopyrite and arsenopyrite using
NBOIT as collector were studied and the results are shown in Fig. 2.
Fig. 2 shows flotation performance of chalcopyrite and arsenopyrite
as a function of NBOIT concentration when the slurry pH was 10. The
results indicate that flotation recovery of chalcopyrite was increased
with increase of NBOIT concentration when it less than 200 mg/L. And
then, flotation recovery of chalcopyrite increased slowly above 93%
with further enhancement of NBOIT concentration. However, in the
whole range of tested collector concentration, the flotation recovery of
arsenopyrite was always below 30%. Therefore, NBOIT had strong
collecting ability and selectivity for chalcopyrite, and good separation
of chalcopyrite from arsenopyrite may be achieved under certain con-
ditions.
Fig. 3 demonstrates the flotation performances of chalcopyrite and
arsenopyrite as a function of slurry pH with NBOIT concentration of
200 mg/L and lime concentration of 7.5 mg/L. The results indicate that
high chalcopyrite recovery was obtained when the slurry pH exceeded
8.5. However, the flotation recovery of chalcopyrite is decreased
sharply when the slurry pH is more alkaline than 10.5. Many studies
have confirmed that oxidation of chalcopyrite occurs and more hy-
droxides appear on its surface (Liu and Laskowski, 1989). The flotation
recovery of arsenopyrite decreases rapidly from 30.3% to 6.0% with
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J. Lu, et al.
Fig. 2. Effect of NBOIT concentration on chalcopyrite and arsenopyrite flota-
tion (pH 10).
Fig. 3. Effect of slurry pH on flotation of chalcopyrite and arsenopyrite (NBOIT
200 mg/L).
increase in pH from 4.25 to 6.05. After that, arsenopyrite flotation re-
covery decreases slowly with further increasing of pH. Thus, the ap-
propriate pH for the separation of chalcopyrite and arsenopyrite is
8.5–10.5.
3.2. Separation of artificially mixed minerals
The separation performance of artificially mixed minerals was in-
vestigated at different NBOIT concentrations. The results are presented
Fig. 4. As the NBOIT concentration increased, the recovery of Cu grows
steadily from 53.9% to 91.2%, while the grade barely decreases from
32.0% to 29.6%. The grade and recovery of As has little change and
always remained at a low level. With NBOIT concentration of 200 mg/
L, the grade and recovery of Cu could reach 31.5% and 90.3%, re-
spectively. The results suggested that an effective separation of chal-
copyrite and arsenopyrite could be achieved with NBOIT collector.
3.3. Zeta potential measurements
The adsorption of reagents on the minerals surfaces usually affects
the surface properties (Xu et al., 2013; Gao et al., 2018; Liu et al.,
2019a; Liu et al., 2019b). Zeta potential measurements were performed
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Minerals Engineering 137 (2019) 118–123
Fig. 4. Effect of NBOIT concentration on separation of artificially mixed mi-
nerals (pH 10, lime 7.5 mg/L).
Fig. 5. Zeta potentials as a function of pH for chalcopyrite and arsenopyrite
with or without NBOIT (NBOIT 200 mg/L).
on chalcopyrite and arsenopyrite before and after the addition of
NBOIT. The results are shown in Fig. 5. Chalcopyrite showed a positive
zeta potential in strong acidic solutions with an IEP of about pH 4.
These zeta potential values are consistent with those reported in lit-
erature (Fullston et al., 1999; Liu et al., 2017; Feng et al., 2018). In the
presence of collector, zeta potentials of chalcopyrite are significantly
shifted to more positive values in the pH range from 3 to 11. This in-
dicated that NBOIT adsorbed on the surface of chalcopyrite. Because
NBOIT is non-ionic, its adsorption could increase the distance of the
shear plane in the electrical double layer from the surface of the mi-
neral, thereby lowering the magnitude of zeta potential. Previous stu-
dies showed similar results, in which the adsorption of non-ionic re-
agents decreased the negative zeta potentials of chalcopyrite (Feng
et al., 2018). However, the zeta potentials of arsenopyrite, and ar-
senopyrite with NBOIT (200 mg/L) did not change. This means that
NBOIT had little impact on arsenopyrite zeta potentials.
3.4. FTIR spectra analysis
FTIR spectroscopy was usually employed to determine the adsorp-
tion behaviors by analyzing the changes of the characteristic peaks
(Zhao et al., 2018; Wu et al., 2018). Therefore, adsorption of NBOIT on
the chalcopyrite and arsenopyrite surfaces was investigated by a FTIR
J. Lu, et al.
Fig. 6. FTIR spectra of chalcopyrite before and after interaction with NBOIT at
pH 10.
Fig. 7. FTIR spectra of arsenopyrite before and after interaction with NBOIT at
pH 10.
spectroscope. FTIR spectra of chalcopyrite and arsenopyrite, NBOIT,
chalcopyrite and arsenopyrite conditioned with NBOIT at pH 10 are
shown in Figs. 6 and 7. In the FTIR spectrum of NBOIT, the bands at
2961 cm−1 and 2874 cm−1 could be attributed to the eCH3 and eCH2
stretching vibration. The bands at 1517 cm−1 and 1170 cm−1were at-
tributed to eC(]S)eNHe and eOeC(]O)eNeCe group vibration
(Leppinen et al., 1988). The bands at around 1064 cm−1 and
1770 cm−1 were assigned to the asymmetric stretching vibration of the
C]S and C]O group (Buckley et al., 2014). After interaction with
NBOIT, the most intense peaks around 2962 cm−1 and 2871 cm−1 arise
from the stretching vibrations ofeCH3 and eCH2 groups in NBOIT
molecules, indicating the NBOIT adsorption on the chalcopyrite surface
(Huang et al., 2018; Zhang et al., 2013). The bands of 1517 cm−1,
1170 cm−1 and 1064 cm−1 in the NBOIT FTIR spectrum shifted to
1507 cm−1, 1173 cm−1 and 1068 cm−1 respectively in the FTIR spec-
trum of chalcopyrite treated with NBOIT. Simultaneously, the char-
acteristic peak of chalcopyrite around 1436 cm−1 shifted to 1458 cm−1.
This demonstrates that the adsorption of NBOIT on the surface of
chalcopyrite is by the chemisorption process. Thus, the chemisorption
may have occurred between NBOIT and the chalcopyrite surface. From
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Minerals Engineering 137 (2019) 118–123
Fig. 8. XPS survey spectra of chalcopyrite and chalcopyrite with NBOIT.
Fig. 7, the characteristic absorption bands of arsenopyrite are at
1637 cm−1, 1127 cm−1 and 435 cm−1, which agree well with the re-
ported data (Henao et al., 2010; Khummalai and Boonamnuayvitaya,
2005). There are no new pronounced bands for arsenopyrite after
treatment with NBOIT, implying weak adsorption for NBOIT on the
arsenopyrite surface. The weak adsorption is the main reason why
NBOIT barely increases the flotation of arsenopyrite.
3.5. XPS analysis
XPS spectroscopy, as a very surface-sensitive analytical technique,
was widely used to measure the changes occurring at the minerals
surfaces in minerals engineering (Fang et al., 2018; Xu et al., 2017;
Zhang et al., 2018). To further confirm the interaction mechanism be-
tween NBOIT and chalcopyrite, XPS analysis of chalcopyrite and chal-
copyrite treated with NBOIT was conducted, and the results are shown
in Fig. 8. It could be found from Fig. 8 that after NBOIT treatment, the N
1s XPS peak was detected on the chalcopyrite surface. The atomic
concentrations of elements C 1s, O 1s, Cu 2p, Fe 2p, S 2p, and N 1s
measured by XPS were summarized in Table 2. Table 2 shows that the N
1s atomic concentration increased from 3.65% of pure chalcopyrite to
4.04% of chalcopyrite treated with NBOIT, indicating that NBOIT
successfully adsorbed on the chalcopyrite surface. Furthermore, the C
1s atomic concentration of chalcopyrite treated with NBOIT increased
2.19%, evidencing that NBOIT adsorbed on to the surfaces of chalco-
pyrite.
To obtain the detailed information about NBOIT attachment, the
chemical status of surface species was further characterized by high
resolution XPS spectra. The Cu 2p3/2 spectra of chalcopyrite and
chalcopyrite treated with NBOIT are illustrated in Fig. 9. The Cu 2p3/2
spectra are fitted by three components at 932.10 eV, 932.80 eV and
934.50 eV, which are assigned to CuFeS2/CuS, CuFeS2/Cu2S and CuO/
Cu(OH)2, respectively (Fairthorne et al., 1998; Acres et al., 2010). The
parameters of the fitted peaks and the percentages of copper occurring
in three surface copper components are shown in Table 3. After NBOIT
treatment, the proportion of the Cu 2p3/2 band at 934.5 eV on chal-
copyrite surface reduced from 3.52% to 2.94%, suggesting that NBOIT
reacted with copper cation and formed new substance.
The high resolution spectra of S 2p for samples are displayed in
Fig. 10. S 2p peaks occur as doublets (S 2p3/2 and S 2p1/2) owing to
spin-orbit splitting (Liu et al., 2015). The S 2p3/2 peaks are twice the
area of the S 2p1/2 peak with a 1.19 eV splitting (Yang et al., 2015).
The parameters of the fitted peaks and the corresponding assigned
species were obtained from the reported data and are shown in Table 4.
The most intense doublet centered at 161.15/162.33 eV is related to the
J. Lu, et al. Minerals Engineering 137 (2019) 118–123

Table 2
Atomic concentration of elements on chalcopyrite surfaces as determined by XPS.
Samples Atomic concentration of elements on chalcopyrite surfaces (%)

C 1s O 1s Cu 2p Fe 2p S 2p N 1s

Chalcopyrite 16.06 37.07 11.36 12.48 19.38 3.65

Chalcopyrite + NBOIT 18.25 28.31 14.61 13.95 20.84 4.04

Table 4
The parameters of fitted peaks and percentages of surface sulfur components in
total sulfur on the samples.
Binding energy (eV) 161.15/ 162.11/ 163.10/ 164.03/
162.33 163.29 164.22 165.21

FWHM (eV) 0.88/0.88 0.88/0.88 0.88/0.88 0.88/0.88

Assignment S2− S2- n S2- 2 Organic S
Chalcopyrite 80.92 14.01 5.07 –
Treated chalcopyrite 1.42 79.05 17.70 1.83

monosulfides (S2−) in CuFeS2. The other two weak doublets positioned

at 162.11/163.29 eV and 163.10/164.22 eV could be attributed to
oxidized sulfur components (polysulfides S2− n and disulfides S2− 2)
(Acres et al., 2010; Harmer et al., 2004; Harmer et al., 2006). After
NBOIT adsorption, the S 2p3/2 spectra may be divided into four com-
ponents, i.e. S2− (161.15 eV), S2- n(162.11 eV), S2- 2(163.10 eV) and
organic S (164.03 eV). The corresponding proportion of these various
species is 1.42%, 79.05%, 17.70% and 1.83%. In the presence of ad-
Fig. 9. High resolution XPS spectra of Cu 2p3/2 ((a) chalcopyrite and (b) sorbed NBOIT only a small part of S2− on the chalcopyrite surface was
chalcopyrite treated with NBOIT). detected. The increase of S2− 2 species at around 163.10 eV from
5.07% to 17.70% (by 12.63%) was far less than that at around
162.11 eV from 14.01% to 79.05% (by 65.04%). This finding implies a
Table 3
The parameters of fitted peaks and percentage of surface copper components in
decreased oxidation of chalcopyrite surfaces after NBOIT coverage. The
total copper on the samples. higher binding energy component at 164.03 eV might represent organic
sulfur in the Cu-NBOIT complex. The strong electron-withdrawing
Binding energy (eV) 932.1 932.8 934.5
ethoxycarbonyl group adjacent to the C]S group decreases the electron
FWHM (eV) 1.1 1.74 1.61 density of sulfur, which improves NBOIT’s selectivity at alkaline con-
Assignment CuFeS2/CuS CuFeS2/Cu2S CuO/Cu(OH)2 ditions. NBOIT’s LUMO (Lowest Unoccupied Molecular Orbital) is
Chalcopyrite 89.57 6.91 3.52 constituted by pz-orbits of every atom in the conjugate eOeC(]O)
Treated chalcopyrite 92.6 4.46 2.94
eNeC(]S)eOe group and willingly accepts strongly d-orbital elec-
trons from Cu(II) or Cu(I) configurations of the copper cation on the
chalcopyrite surface. Hence, the interaction of NBOIT with the copper
cation involves forming a six-membered chelate ring, and the collecting
power of NBOIT for chalcopyrite and its selectivity are improved at the
same time (Liu et al., 2006; Shen et al., 1998). Based on the results and
analyses mentioned above, a schematic adsorption model of NBOIT on
chalcopyrite surfaes was suggested in Fig. 11.

4. Conclusion

In the present work, we found that a novel reagent N-

Butoxycarbonyl-O-Isobutyl Thiocarbamate (NBOIT) as a collector along

Fig. 10. High resolution XPS spectra of S 2p spectra ((a) chalcopyrite and (b)
chalcopyrite treated with NBOIT).

Fig. 11. The suggested chemisorption model of NBOIT on chalcopyrite surfaces.

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with lime as a depressor, can achieve the selective separation of chal-
copyrite from arsenopyrite in the flotation of mixed binary minerals at
pH 10. Diverse analytical methods, including zeta potential measure-
ments, FTIR spectroscopy and XPS analysis were employed to elucidate
the adsorption mechanism. Based on the analysis, we draw the fol-
lowing conclusions:
(i) NBOIT has strong collecting ability and selectivity for chalcopyrite.
(ii) Selective chemisorption of NBOIT on to chalcopyrite occurs in the
form of a Cu-NBOIT complex on the surface of chalcopyrite.
In summary, NBOIT can selectively adsorb on the chalcopyrite
surface involving intense chemisorption, while NBOIT exhibits weak
adsorption to arsenopyrite. The adsorption can promote the hydro-
phobicity of the chalcopyrite surface, which is very important for a
successful separation. It has great potential to be applied industrially to
deal with abundant complicated chalcopyrite bearing ore, especially
those associated with arsenopyrite.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (51704057); the Fundamental Research Funds for
the Central Universities (N170104018); the China Postdoctoral Science
Foundation (2017 M621153); and the Postdoctoral Science Foundation
of Northeastern University (20170312).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.mineng.2019.04.003.
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