Chemical Engineering Science 205 (2019) 220–229

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Chemical Engineering Science

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

Investigating the selectivity of a xanthate derivative for the flotation

separation of chalcopyrite from pyrite
Xiaoping Huang, Kaihua Huang, Yun Jia, Shuai Wang, Zhanfang Cao ⇑, Hong Zhong ⇑
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

The synthesis of a novel xanthate SIBX HEIBX

derivative (HEIBX) and its application
in the separation of chalcopyrite from
pyrite.

The molecular behaviour of HEIBX
and SIBX were compared by DFT
calculation.

Properties of HEIBX were compared
with properties of another surfactant
SIBX.

HEIBX exhibited superior collector
ability and selectivity for chalcopyrite
against pyrite than SIBX.

HEIBX chemisorbed on the surface of
chalcopyrite by formation of CuAO
and CuAS bonds.

a r t i c l e i n f o a b s t r a c t

Article history: Separating chalcopyrite, an important copper-containing ore, from pyrite is an important mineral-
Received 17 January 2019 processing objective. Herein, we report the synthesis of S-hydroxyethyl-O-isobutyl xanthate (HEIBX), a
Received in revised form 19 April 2019 novel surfactant bearing both hydroxyl and thione groups, through the attachment of a hydroxyethyl
Accepted 30 April 2019
group to sodium isobutyl xanthate (SIBX), and its first application as a flotation collector for the selective
Available online 2 May 2019
flotation-separation of chalcopyrite from pyrite. The flotation mechanism involving HEIBX and chalcopy-
rite or pyrite was investigated by DFT calculations, UV–vis spectroscopy, contact-angle and surface-
Keywords:
tension measurements, flotation and zeta-potential experiments, as well as FTIR spectroscopy and XPS.
Chalcopyrite
Pyrite
Incorporation of the hydroxyethyl group was observed to increase the molecular properties of SIBX by
Xanthate increasing the number of active sites, arrangement density, selectivity and hydrophobicity, thereby
Flotation improving its flotation performance. Chalcopyrite was separated from pyrite using 4  105 molL1
Separation HEIBX at pH 8.0. Furthermore, we found that the hydroxyl and thione functional groups adsorb onto
the chalcopyrite surface though the formation of CAOACu and CASACu bonds.
Ó 2019 Published by Elsevier Ltd.

1. Introduction
Xanthate is an important chemical product that has been
widely used in the medical, agriculture, wastewater-treatment
and functional-materials industries (Besada et al., 2018; Wang
⇑ Corresponding authors.
E-mail addresses: zfcao1980@163.com (Z. Cao), zhongh@csu.edu.cn (H. Zhong).
et al., 2017; Chand et al., 2015; Carta et al., 2013; Kaltenhauser
et al., 2013). Since it was first introduced into the minerals-
processing industry by Keller, xanthate has become the most
important flotation collector for sulfide ores, as well as oxide min-
erals, facilitating their separation from non-valuable gangue
(Ejtemaei and Nguyen, 2017; Mustafa et al., 2004). As the most
widely used xanthate in flotation applications, sodium isobutyl
xanthate (SIBX) is inexpensive, very soluble, and exhibits a strong

https://doi.org/10.1016/j.ces.2019.04.051
0009-2509/Ó 2019 Published by Elsevier Ltd.
 X. Huang et al. / Chemical Engineering Science 205 (2019) 220–229
collecting ability. However, its poor selectivity makes it difficult to
meet the flotation-recovery requirements of increasingly complex
minerals. Consequently, SIBX has been modified in order to
improve its flotation selectivity.
In general, transforming an ionic xanthate into a non-ionic com-
pound can significantly increase its selectivity and helps to sepa-
rate chalcopyrite from pyrite, which is a difficult problem. For
instance, the Dow Chemical Co. prepared O-isopropyl-N-
ethylthionocarbamate (IPETC) from sodium isopropyl xanthate
(SIPX), chloroacetic acid, and ethylamine. The compound proved
to be a superior collector for the separation of chalcopyrite from
pyrite (Fairthorne et al., 1997). N-Allyl-O-alkyl thionocarbamates
(ATCs) are derivatives of xanthates that have been used worldwide
for the industrial flotation and separation of chalcopyrite from pyr-
ite, due to its superior selectivity toward copper sulfide minerals
(Sheridan et al., 2002).
Recently, some novel xanthate derivatives have been prepared
by introducing additional active sites into the molecule. These
modified molecules usually exhibited excellent collecting abilities
and selectivities, and were able to efficiently separate copper sul-
fide minerals from pyrite. Ma et al. (2017) synthesized a novel
compound (BIBX) from sodium isobutyl xanthate (SIBX) and ben-
zoyl chloride. BIBX exhibited better collecting ability and selectiv-
ity for chalcopyrite than SIBX. Xiao et al. (2017) prepared the novel
IPXPO collector, which bears thione and oxime groups, from
sodium isopropyl xanthate (SIPX) through a series of reactions.
Experimental results reveal that IPXPO is an excellent collector
for chalcopyrite. In view of the excellent flotation performance of
the above-mentioned collector, the development of novel xanthate
ester surfactants bearing two chelating groups as flotation collec-
tors is conceptually interesting.
S-Hydroxyethyl-O-isobutyl xanthate (HEIBX) is a SIBX deriva-
tive that contains both C@S and AOH groups; HEIBX is prepared
by reacting sodium isobutyl xanthate with ethylene chlorohydrin.
This compound exhibits superior dispersibility and has been used
as a lubricant additive (Wang et al., 2015; Kato, 1994). Since it
bears hydrophobic and chelating groups, HEIBX can be used as a
flotation collector; however, to the best of our knowledge, its use
in flotation has never been reported.
In this study, we prepared HEIBX and report its first use as a
flotation collector for the selective separation of chalcopyrite from
pyrite. We also systematically investigated the adsorption mecha-
nism of HEIBX onto the surface of chalcopyrite and pyrite. DFT cal-
culations, surface-tension, UV–vis spectroscopy and contact-angle
experiments were used to compare the molecular and surface
behaviour of HEIBX and SIBX. The collecting abilities of the two
surfactants were examined by single-mineral flotation experi-
ments. Finally, zeta-potential experiments, FTIR spectroscopy,
(a)
Intensity
Chalcopyrite(CuFeS2)-83-0983
10 20 30 40 50
2 Theta (°)
Fig. 1. XRD patterns of (a) chalcopyrite and (b) pyrite.
221
and XPS were used to study the mechanisms for the adsorption
of HEIBX onto chalcopyrite and pyrite.
2. Materials and methods
2.1. Materials and reagents
Analytically pure ethylene chlorohydrin, hydrochloric acid,
sodium hydroxide and 4-methyl-2-pentanol (MIBC) were pur-
chased from the Xiya Reagent Co. Ltd (Shandong, China). Sodium
isobutyl xanthate (SIBX, purity = 93.1%) was obtained commer-
cially; Cu2+, Fe2+, and Fe3+ were derived from analytically pure
CuSO45H2O, FeSO47H2O, and Fe2(SO4)3. In particular, Cu+ was pro-
duced by reducing Cu2+ ions with 1.1 M equivalents of ascorbic
acid.
Pure chalcopyrite and pyrite mineral samples were purchased
from the Daye, Hubei, China. After crushing, grinding, and screen-
ing, the ore samples were classified according to the desired parti-
cle size, namely <38 mm, and >38 mm but <76 mm. Ore with the
former particle size was used in the zeta potential experiments,
as well as for FTIR spectroscopy and XPS, while that with the latter
particle size was used in micro-flotation experiments. The purity of
the two ores were determined by XRD and XRF using the ore with
<38 mm particle size, the results of which are displayed in Fig. 1 and
listed in Table S1. The XRD and XRF data reveal that the chalcopy-
rite and pyrite were 96.56% and 94.69% pure, respectively. The
minerals were ultrasonically cleaned prior to each experiment.
2.2. Methods
2.2.1. Synthesis of S-hydroxyethyl-O-isobutyl xanthate (HEIBX)
S-Hydroxyethyl-O-isobutyl xanthate (HEIBX) was synthesized
from SIBX and ethylene chlorohydrin as shown in Fig. S1: SIBX
(0.1 mol, 19.32 g) and ethylene chlorohydrin (0.1 mol, 8.13 g) were
mixed in a 150 mL three-necked glass flask and mechanically stir-
red at 25 °C. Distilled water (15 mL) was then added to the mix-
ture, after which it was stirred at 50 °C for 7 h. The mixture was
then cooled to room temperature and extracted with dichloro-
methane (3  30 mL). After drying over Na2SO4, the solvent was
evaporated in vacuo to afford the crude product, which was sepa-
rated by column chromatography (5:1 v/v n-hexane/ethyl acetate)
to give the desired product.
2.2.2. DFT calculations
The initial molecular structures of HEIBX and the SIBX anion
were first optimized using MM2 and PM3 methods in ChemBioOf-
fice 2014 (Deng et al., 2016). The optimized structures were then
further optimized at the 6-311+G(d) (DFT) level of theory using
(b)
Intensity
Pyrite (FeS2)-71-1680
60 70 10 20 30 40 50 60 70
2 Theta (°)
222 X. Huang et al. / Chemical Engineering Science 205 (2019) 220–229
Gaussian 09 (Kaczor and Proniewizc, 2004; Zhao et al., 2013). In
addition, IEF-PCM (the integral equation formalism for the polariz-
able continuum model) was used as the solvation model. Water
was chosen as the solvent and its dielectric constant was set as
78.36 (Huang et al., 2019; Yang et al., 2018).
2.2.3. Surface tension measurements
The surface tensions of HEIBX and SIBX were measured using a
QBZY surface tension meter (Fangrui Instrument Co., Ltd, Shanghai,
China) by the Wilhelmy plate method at 25 °C. In order to avoid the
effects of residues, the platinum plate was cleaned successively
with alcohol and water, and then flame dried. The surface-
tension data are averages of five measurements determined under
automated operating condition. The relationship between surface
tension and the logarithm of the concentration was plotted. The
critical micelle concentration (CMC) value was obtained by extrap-
olating two straight lines on the linear parts of the curve until
intersected each other. The intersection was deemed to be the
value of the CMC (Budi et al., 2010; Yu et al., 2010).
2.2.4. UV–vis spectroscopy
To evaluate the selective interactions operating between HEIBX
or SIBX and Cu2+, Cu+, Fe2+ or Fe3+ in solution, the samples were
subjected to UV–vis spectroscopy in the 200–350 nm range with
a UV-1750 spectrophotometer (Shimadzu, Japan). Equal volumes
(25 mL) of aqueous solutions of HEIBX or SIBX (2  104 molL1)
and Cu2+, Cu+, Fe2+ or Fe3+ (2  104 molL1) were mixed in a
150 mL conical flask. After stirring for 20 min at 25 °C, the mixture
was filtered through a filter with 0.45 lm pore diameter for UV–vis
spectroscopy.
2.2.5. Surface wettability experiments
The contact angles of water droplets on the surfaces of chal-
copyrite and pyrite were measured using a JC2000C contact angle
analyzer (Shanghai Zhongchen Co., China) by the water-drop cap-
tive method. Chunk samples of chalcopyrite and pyrite were pol-
ished with abrasive paper, and then successively ultrasonically
cleaned for 5 min in ethanol and distilled water. After drying with
pure N2, the chalcopyrite and pyrite samples were used to measure
water contact angles. The data presented are averages of five inde-
pendent measurements and the error bars represent standard
deviations of several parallel experimental results.
2.2.6. Micro-flotation experiments
Micro-flotation experiments were performed using an XFGII
flotation machine (Jilin Exploration Machinery Plant, China). The
volume of the flotation cell was 30 mL and the stirring speed of
the machine was fixed at 1650 rpm. In each experiment, 2.0 g of
ore sample and a specific amount of water were added into the cell
and stirred for 3 min. In the meantime, the pH of the pulp was
adjusted to the required value using hydrochloric acid and sodium
hydroxide. A collector solution of the appropriate concentration
was added and the mixture was stirred for a further 3 min, after
which, a solution of MIBC (frother) was added into the slurry, with
stirring continued for 1 min. Finally, the flotation test was con-
ducted for 5 min. The concentrates and tailings were collected
and dried for flotation-recovery calculations.
2.2.7. Zeta potential measurements
The zeta potentials of chalcopyrite and pyrite before and after
treatment with HEIBX were measured using a JS94H electrophore-
sis apparatus (Beckman Coulter Inc., USA). In each experiment,
0.05 g of chalcopyrite or pyrite was added to 50 mL 1  103
molL1 solution of potassium nitrate with or without 5  105
molL1 HEIBX. The pH of the mixture was adjusted using nitric
acid or potassium hydroxide solutions. The results presented are
averages of three independent experiments and the error bars rep-
resent standard deviations of several parallel experimental results.
2.2.8. Characterization techniques
The FTIR spectra of chalcopyrite and pyrite before and after
treatment with HEIBX solution were recorded on an FTIR-740
infrared spectrometer (Nicolet, USA) in the 4000–400 cm1 range
using the KBr disk method. A 0.5 g sample of chalcopyrite or pyrite
was added into 50 mL of a 1  104 molL1 HEIBX aqueous solu-
tion, or 50 mL of pure water. The mixture was shaken in a 30 °C
thermostat water baths for 2 h, then filtered, and the solid sample
collected in this manner was washed with distilled water and dried
in a vacuum oven for 24 h.
Chalcopyrite was subjected to XPS before and after HEIBX treat-
ment using a Thermo Fisher ESCLAB 250Xi spectrometer (Thermo
Fisher, USA). The pass energy was set as 30 eV with a monochrom-
atized Al Ka X-ray source operating at 150 W and between 1010
and 107 Torr.
3. Results and discussions
3.1. Characterization of HEIBX
The structure of HEIBX was characterized by FTIR (Fig. 9), 1H
NMR (Fig. S2) and 13C NMR spectra (Fig. S3); the results were listed
as follows: yield: 83.2%. FTIR (KBr, cm1): 3360 (mOH), 2963 (mCH3),
2934, 2875 (mCH2), 1469 (mC(=S)-S), 1221 (mC-O-C), 1061 (mC=S), 929
(mC-S); 1H NMR (400 MHz, CDCl3-d3): d (ppm) 0.94 (d, 6H, CH3),
1.63 (s, 1H, OH), 2.08 (dp, 1H, CH), 3.30 (t, 2H, -SCH2), 3.83
(t, 2H, CH2-OH), 4.30 (t, 2H, CH2); 13C NMR (400 MHz, CDCl3-d3):
d (ppm) 19.11 (2CH3), 27.66 (CH), 38.32 (S-CH2), 60.74 (CH2-OH),
76.8 (CH2-O), 214.67 (C@S).
3.2. Molecular level behaviour
Understanding the behaviour of molecules is important for pre-
dicting their flotation abilities and selectivities. Therefore, we stud-
ied the molecular level behaviour of HEIBX and SIBX by DFT,
surface-tension experiments, and UV–vis spectroscopy.
3.2.1. DFT calculations
Recently, the density functional theory (DFT) method has been
widely used to evaluate possible collector/mineral interaction
mechanisms due to its reliability and cost effectiveness (Long
et al., 2016). The physicochemical properties of collectors can be
obtained by calculating the structures of collector molecules.
Therefore, the structures of HEIBX and the SIBX anion were calcu-
lated at the B3LYP/6-311+G(d) level of theory (Yang et al., 2018; Jia
et al., 2019), the results of which are shown in Fig. S4. The chemical
reactivities of HEIBX and SIBX anion were evaluated by comparing
their molecular electrostatic potentials, frontier molecular orbitals,
and dipole moments.
The molecular electrostatic potential (MEP) and the associated
color-graded map is an important tool for analyzing the functional
sites of a molecule and predicting the interactions of its reactive
sites (Hesabi and Behjatmanesh-Ardakani, 2018). The most nega-
tively charged regions in the MEP map are colored red and are
the preferred site for electrophilic attack, while the most positive
regions (for nucleophilic attack) are colored blue. The various col-
ors reflect the magnitude of the electrostatic potential and fol-
lowed the order: red < orange < yellow < green < blue. The color
coding in these maps range between 0.06 (deepest red) and
+0.06 a.u. (deepest blue). The MEP maps of the two collectors are
shown in Fig. 2, which reveals two red regions in the HEIBX mole-
cule, located at the C@S and AOH groups, while the SIBX anion
 X. Huang et al. / Chemical Engineering Science 205 (2019) 220–229
Fig. 2. MEP maps for HEIBX and the SIBX anion.
exhibits only two yellow regions centered on the C@S and CAS
groups, indicative of weaker nucleophilicity. These results show
that the C@S and AOH groups of HEIBX, and the C@S and CAS
groups of the SIBX anion can donate their electrons to metal
cations. The Mulliken charges of selected atoms of the two collec-
tors were also calculated and are listed in Table 1. The results
reveal that negative charges are mainly centered on the O11 and
S7 atoms of HEIBX, and the S7 and S8 atoms of the SIBX anion
(Fig. 3). In addition, the S atom of the C@S group in HEIBX is more
negatively charged than that in the SIBX anion. These results fur-
ther demonstrate that the active groups of HEIBX are the C@S
and AOH groups, while those of the SIBX anion are the C@S and
CAS groups, and that the electron-donating ability of HEIBX is
greater than that of the SIBX anion.
Frontier molecular orbitals (FMOs) theory is a well-known
method for qualitatively predicting chemical-reactivity character-
istics (Sevvanthi et al., 2018). Therefore, it is often used to investi-
gate the reactivity of a surfactant in order to provide guidance on
its use in the flotation industry (Deng et al., 2016; Yang et al.,
2018). The highest occupied molecule orbital (HOMO) provides
information on the electron-donating ability of a collector to a
metal or mineral surface, while the lowest unoccupied molecule
orbital (LUMO) provides information on the electron-accepting
ability of a collector toward the d-orbital electrons of a metal spe-
cies (Yang et al., 2018; Balachandran et al., 2013). The higher the
HOMO energy, the more likely it is to donate electrons. Conversely,
a higher LUMO energy reveals a weaker affinity for electrons. The
calculated HOMO and LUMO energies are listed in Table 1. The
HOMO energy of HEIBX (0.2466 a.u) was calculated to be higher
than that of the SIBX anion (0.2593 a.u), which suggests that
HEIBX is more strongly able to donate electron toward metal atoms
(Hesabi and Behjatmanesh-Ardakani, 2018). In addition, the LUMO
energy of HEIBX (0.0634 a.u) is higher than that of the SIBX anion
(0.0697 a.u), signifying the electron-accepting ability of the SIBX
anion toward the d-orbital electrons of metal ions is greater than
that of HEIBX. Fig. S5 shows the LUMO and HOMO maps of the
two collectors, which reveals that the S7 atom of the C@S group
in each collector is the main contributor to the HOMO, indicating
its potential involvement in bond formation between the C@S
group and the metal ions on the mineral surface. In addition, the
LUMO is distributed over O5, C6, and S7 atoms of HEIBX, and the
O5 and C6 atoms of the SIBX anion, suggesting that these atoms
can accept d-orbital electrons from metal atoms.
Table 1
HOMO and LUMO (energies), dipole moments, and selected atomic charges of HEIBX and the SIBX anion.
Species Energies (a.u)a
HOMO LUMO
HEIBX 0.2466 0.0634
SIBX anion 0.2593 0.0697
a
1a.u = 2625.500 kJmol1.
223
Fig. 3. Schematic representation of the HEIBX molecule and the SIBX anion, with
selected atoms numbered.
Dipole moment, as a measure of molecular polarity, can be used
to evaluate electrostatic and van der Waals interactions between
collectors and metal species (Deng et al., 2016; Zhao et al., 2013).
Generally speaking, the collector with the larger dipole moment
interacts more readily with metal ions on mineral surfaces. The
calculated dipole moments of SIBX anion and HEIBX are presented
in Table 1, which reveals that HEIBX (5.1150 Debye) has a larger
dipole moment than the SIBX anion (4.8741 Debye), which shows
that HEIBX can interact more strongly through electrostatic and
van der Waals interactions with metal species than the SIBX anion
(Zhao et al., 2013).
The above DFT results show that attachment of the hydrox-
yethyl group to SIBX converting it to HEIBX increases the number
of reactive sites and enhance its electron-donating ability, which
may affect its flotation performances.
3.2.2. Surface tension, saturation adsorption and minimum area per
molecule
The surface activity of a surfactant is an important parameter
for froth flotation, and can be evaluated by measuring its surface
tension (Huang et al., 2014). Therefore, we measured the surface
tensions of HEIBX and SIBX in aqueous solution, with the relation-
ships between the surfactant concentration (log(C)) and the sur-
face tension (c) at pH 8.0 displayed in Fig. 4. In addition, the
values of various surface parameters, including Umax (saturation
adsorption, molm2) and Amin (average minimum area per mole-
cule, nm2) were calculated using Eqs. (1) and (2) (Menger et al.,
2000; Ghosh and Chakraborty, 2007) are summarized in Table 2.
 
103 @c
Cmax ¼  ð1Þ
2:303nRT @logC T
1018
Amin ¼ ð2Þ
Cmax NA
In Eqs. (1) and (2), c is the surface tension (mNm1),
(oc/ologC)T is the slope (12.10 for HEIBX and 7.02 for SIBX) of
the curve of the surface tension vs. log(C) curve below the critical
micelle concentration (CMC) (Huang et al., 2014; Ghosh and
Chakraborty, 2007), T is the experimental temperature (298.15
K), R is the gas constant (8.314 Jmol1K1), the factor 2.303 is
the value of the natural logarithm of 10, NA is the Avogadro num-
ber (6.02  1023), n is a constant which depends on the number of
surfactant species adsorbed at the interface (Alami et al., 1993).
Generally, n = 2 for a single-collector system (Tian et al., 2017).
Dipole moment (Debye) Mulliken charge
Atomic charge
5.1150 O5:0.3189; C6:0.0603; S7:0.5419; S8:0.1923; O11:0.4341
4.8741 O5:0.2612; C6:0.0965; S7:0.1233; S8:0.2816
224 X. Huang et al. / Chemical Engineering Science 205 (2019) 220–229

75
( N -1)

70
1
i (mN·m

65

60
tension

55
HEI BX
50 SIB X B(-0.26,44.13)
45
Surface

40
f

A(-2.20,34.67)
35
S

30
-6 -5 -4 -3 -2
-1
Log (C/mol·L )
Fig. 4. Relationships between surfactant concentration and surface tension at pH
8.0.
As shown in Table 2, the CMC of HEIBX is greater than that of
SIBX, while the cCMC value of HEIBX is smaller than that of SIBX,
suggesting that HEIBX is more hydrophobic compared to SIBX.
Umax and Amin are used to evaluate the amount of surfactant
adsorbed on a mineral surface; a greater Umax value or a smaller
Amin value indicates a denser arrangement of surfactant molecules
on the mineral surface (Tian et al., 2017). Table 2 reveals that
HEIBX has a greater Umax value and a smaller Amin value than SIBX,
suggesting that HEIBX molecular is more densely arranged on the
mineral surface than SIBX. The adsorptions of SIBX and HEIBX on a
mineral surface are schematically presented in Fig. 5.
3.2.3. UV–vis spectroscopy
Chalcopyrite, a major copper resource, is often found in associ-
ation with pyrite (Owusu et al., 2014). Separating chalcopyrite
from pyrite is therefore an important step in the production of cop-
per. Hence, in order to compare the selectivities of HEIBX and SIBX
toward chalcopyrite and pyrite, interactions between HEIBX or
SIBX and Cu2+, Cu+, Fe2+ or Fe3+ were investigated by UV–vis spec-
troscopy. As shown in Fig. 6(a), the UV spectra of HEIBX are signif-
icantly different before and after treatment with Cu2+ and Cu+,
while the UV spectra were almost unchanged before and after
treatment with Fe3+ and Fe2+, suggesting that HEIBX interacts
selectively with Cu2+ and Cu+, but not with Fe2+ and Fe3+. The spec-
tra of SIBX before and after metal ions treatment are shown in
Fig. 6(b). The spectrum of SIBX significantly changed upon treat-
ment with Cu2+, Cu+, Fe2+, and Fe3+, revealing the existence of
strong interactions between SIBX and Cu2+, Cu+, Fe2+, and Fe3+.
Based on the DFT results, the surface tension and UV–vis spec-
troscopy data, we conclude that HEIBX will selectively interact
with chalcopyrite, but not with pyrite, while SIBX will interact with
both chalcopyrite and pyrite. Furthermore, the amount of HEIBX
adsorbed on the chalcopyrite surface is expected to exceed that
of SIBX.
3.3. Surface wettability studies
In general, hydrophobic minerals tend to be more floatable.
Consequently, the effect of the collector on the hydrophobicity of
-1 0 Fig. 5. Illustrating the adsorption of SIBX and HEIBX adsorption on a mineral
surface.
the mineral surface needs to be studied. Contact-angle data pro-
vide a measure of the hydrophobicity of a surface. Therefore, we
measured the contact angles of water droplets on the surfaces of
chalcopyrite and pyrite as functions of collector concentration (at
pH 8.0), the results of which are presented in Fig. 7. The untreated
chalcopyrite and pyrite surfaces exhibited water contact angles of
73.5 ± 1.5° and 53.5 ± 2.1° (Fig. S6), respectively, which are very
close to the reported values (Liu et al., 2016; Hirajima et al.,
2017; Deng et al., 2017). The contact angle increased to
92.5 ± 1.2° for chalcopyrite and 58.0 ± 0.5° for pyrite as the HIEBX
concentration was increased from 0 to 6  105 molL1. These
results indicate that HEIBX has a stronger effect on the hydropho-
bicity of the chalcopyrite surface than the pyrite surface. The
contact angles on both the chalcopyrite (88 ± 2.6°) and pyrite
(85.0° ± 1.9°) surfaces were also observed to increase as the SIBX
concentration was increased from 0 to 6  105 molL1. In addi-
tion, we found that HEIBX increased the hydrophobicity of the
chalcopyrite surface more than SIBX, but it was much less able to
increase the hydrophobicity of pyrite compared to SIBX. This
behavior contributes to the difference in the selectivities of the
two collectors toward the two minerals.
3.4. Flotation experiments
In view of the difference in the molecular properties of the two
collectors and their effects on the hydrophobicities of the two min-
eral surfaces described above, we expected to be able to apply
them to the flotation separation of chalcopyrite from pyrite; hence,
flotation experiments were conducted. The effects of pulp pH and
collector concentration on flotation are displayed in Fig. 8. Fig. 8
(a) reveals that the flotation recovery of chalcopyrite using each
collector first increased and then decreased as the pulp pH was
increased from 2.0 to 11.0. This may be due to the iron on the chal-
copyrite surface oxidizing more readily to iron hydroxide under
extremely alkaline or acidic conditions, to form an overlayer on
the mineral surface. The overlayer prevents interactions between
the mineral and the collector, resulting in poor flotation recovery.
Oxidation is less likely to occur under neutral condition; hence,
the collector is more easily adsorbed on the mineral surface at a
pH of around 8.0 (Fairthorne et al., 1997; Chander 1991). Chalcopy-
rite flotation recoveries of 91.16% for HEIBX and 86.99% for SIBX

Table 2
Values of important parameters for HEIBX and SIBX.

Surfactant CMC (molL1) cCMC (mNm1) Umax (molm2) Amin (nm2)

3 6
HEIBX 6.82  10 34.67 1.06  10 1.57
SIBX 5.50  101 44.13 6.15  107 2.70
 X. Huang et al. / Chemical Engineering Science 205 (2019) 220–229 225

1.5
(a) HEIBX 1.2 (b) SIBX
HEIBX+Cu2+ SIBX+Cu2+
1.0
HEIBX+Cu+ SIBX+Cu+
1.0
HEIBX+Fe2+ SIBX+Fe2+
Absorbance

0.8

Absorbance
HEIBX+Fe3+ SIBX+Fe3+
0.6
0.5
0.4

0.2
0.0
0.0

200 225 250 275 300 325 350 200 225 250 275 300 325 350

Wavelength (nm) Wavelength (nm)

Fig. 6. UV–vis spectra of (a) HEIBX and (b) SIBX before and after treatment with metal ions.

100 thereby resulting in poor flotation recovery. The recovery using

HEIBX was always much lower than that obtained with SIBX over
90 the entire pH range. The flotation recoveries of pyrite by SIBX and
HEIBX were 40.13% and 11.36%, respectively, at pH 8.0. In addition,
80 the natural floatabilities of the two minerals at various pH values
in the absence of collector treatment were investigated. Pyrite
Contact angle

70 was found to be more hydrophilic than chalcopyrite in the exper-

imental pH range. The addition of either collector has an impact on
60 the flotation of chalcopyrite and pyrite, with SIBX improving the
flotation of pyrite more than HEIBX.
50 Fig. 8 (b) shows the effect of the collector concentration on the
Chalcopyrite Pyrite
flotation of chalcopyrite and pyrite at pH 8.0. The collector concen-
40 HEIBX
tration influences the flotation recovery of chalcopyrite signifi-
SIBX cantly, which sharply increased as the collector concentration
30
0 20 40 60 80
was increased from 0 to 2  105 molL1; further increases in col-
lector concentration had little effect on the flotation results. The
C (×10 mol·L )
-6 -1
chalcopyrite flotation recoveries were 93.94% for HEIBX and
89.27% for SIBX at concentrations of 4  105 molL1, which indi-
Fig. 7. Contact angles of water on the chalcopyrite and pyrite as functions of
collector concentration at pH 8.0. cates that HEIBX has a stronger collecting ability for chalcopyrite
than SIBX, in agreement with the DFT results. The flotation results
for pyrite using the two collectors are quite different. The flotation
were obtained at their optimization pH of 8.0. On the other hand, recoveries of pyrite increased from 4.76% to 24.39%, and from
the flotation recovery of pyrite was observed to decrease with 4.76% to 64.31% using HEIBX and SIBX, respectively, as the collector
increasing pulp pH using both collectors, which is possibly due concentrations were increased from 0 to 4  105 molL1, demon-
to the fact that pyrite is easily oxidized to Fe(OH)3 in aqueous solu- strating that SIBX recovers more pyrite than HEIBX at pH 8.0. The
tions (Li et al., 2018) and that Fe(OH)3 covers the pyrite surface and flotation results reveal that HEIBX has a superior collecting ability
hinders interactions between the collector and the pyrite surface, for chalcopyrite than SIBX and that its flotation selectivity for

100
(a) 100 (b)
80
HEIBX+Ch 80
SIBX+Ch
Recovery /%

60
Recovery /%

HEIBX+Py Ch HEIBX+Ch
60
SIBX+Py SIBX+Ch
40 Py
40

20
20
HEIBX+Py
0 0 SIBX+Py

2 4 6 8 10 12 0 20 40 60 80
pH -6 -1
C (×10 mol·L )
Fig. 8. Effect of (a) pulp pH (collector concentration: 2  105 molL1) and (b) collector concentration (pH = 8.0) on the flotation recoveries of chalcopyrite (Ch) and pyrite
(Py).
226 X. Huang et al. / Chemical Engineering Science 205 (2019) 220–229

chalcopyrite over pyrite is better than that of SIBX at a pH of cies. The zeta potential of pyrite before and after HEIBX treatment
around 8.0. Apparently, the introduction of the hydroxyethyl group is shown in Fig. 9(b); the IEP value of pure pyrite was 5.33, which
onto SIBX increases its collecting ability and selectivity, such that was in agreement with previously reported results (Yin, W., Xue, J.,
chalcopyrite can be flotation separated from pyrite using 4  et al., 2018; Yin, Z., Hu, Y., et al., 2018; Basanayaka et al., 2017). The
105 molL1 HEIBX at pH 8.0. The interactions between the col- zeta potential of pyrite was insignificantly different after treatment
lector and the mineral reflect interfacial behavior. with HEIBX, suggesting that HEIBX is weakly adsorbed onto the
pyrite surface. The observed changes of zeta potential confirm that
3.5. Investigating the adsorption mechanisms HEIBX adsorbs selectively onto the chalcopyrite surface.

Compared to SIBX, HEIBX exhibited superior collecting ability 3.5.2. FTIR spectroscopy
and selectivity for chalcopyrite; therefore, exploring the mecha- The FTIR spectra of the various samples are presented in Fig. 10.
nism for the adsorption of HEIBX onto chalcopyrite and pyrite by HEIBX exhibits a characteristic peak at around 3360 cm1, which is
zeta potential measurements, FTIR spectroscopy, and XPS, is a assigned to the stretching vibration of the ACOAH group (Ermis
meaningful objective. et al., 2018), and bands at 2963, 2934, and 2875 cm1, which are
attributed ACH3 and ACH2A stretching vibrations, respectively
3.5.1. Zeta potential measurements (Tobón et al., 2009). The band at 1469 cm1 is assigned to the AC
It is well-known that the adsorption of a collector on a mineral (@S)ASA stretching vibration (Ma et al., 2017), while the bands
surface can change the surface charge of that surface (Yin, W., Xue, at 1221, 1061, and 934 cm1 are due to CAOAC, C@S, and C-S
J., et al., 2018; Yin, Z., Hu, Y., et al., 2018). Therefore, studying stretching vibration, respectively (Huang et al., 2017; Juncal
changes in the mineral surfaces is a useful strategy for elucidating et al., 2015). The FTIR results are consistent with the structure of
the collector-adsorption mechanism of the active sites of the sur- HEIBX. The HEIBX-chalcopyrite complex (Fig. 10(a)) exhibits char-
face. The zeta potentials of chalcopyrite and pyrite before and after acteristic chalcopyrite-surface ACH3, ACH2, and CAS peaks at
treatment with 5  105 molL1 HEIBX, as functions of pH, are 2963, 2934, 2875, and 934 cm1, suggesting that HEIBX is
shown in Fig. 9, which reveals that pure chalcopyrite has an iso- adsorbed on the chalcopyrite surface. The ACOAH band of HEIBX
electric point (IEP) of 5.96 (Fig. 9(a)), which is very close to previ- is almost absent and a new peak, which is assigned to CAOACu,
ously reported values (Mitchell et al., 2005; He et al., 2016). is evident at 512 cm1, consistent with the reported value
Following treatment with HEIBX, the chalcopyrite zeta potential (Khusnun et al., 2018). Meanwhile, the band originally at 1221
shifted to a more negative value, with an IEP value of around cm1, which is due to the CAOAC stretching vibration, shifted to
5.00, indicating that HEIBX is chemisorbed onto the chalcopyrite a higher frequency (1282 cm1), demonstrating that the CAOAC
surface through interactions with positively charged copper spe- electron density had changed. These results indicate that the

40
80 (a) (b)
60
Chalcopyrite 20 Pyrite
Chalcopyrite with HEIBX Pyrite with HEIBX
Zeta potential /mV

Zeta potential /mV

40
0
20 (5.33, 0)
(5.96, 0)
0 -20

(5.00, 0)
-20
-40
-40

-60 -60
2 4 6 8 10 12 2 4 6 8 10 12

pH pH
Fig. 9. Zeta potentials of (a) chalcopyrite and (b) pyrite before and after treatment with HEIBX as functions of pH.

(a) HEIBX+Chalcopyrite (b)

HEIBX+Pyrite
2963

2875
2934

1520

934
512
Transimittance /%

Transimittance /%
1282

1631

1081
3434

Chalcopyrite
Pyrite

HEIBX
1631

1081
1061 934
1469
3360

2875

3434
2934
2963

1221

4000 3600 3200 2800 2400 2000 1600 1200 800 400 4000 3600 3200 2800 2400 2000 1600 1200 800 400

Wavenumber /cm -1
Wavenumber /cm-1

Fig. 10. FTIR spectra of (a) chalcopyrite and (b) pyrite before and after treatment with HEIBX.
 X. Huang et al. / Chemical Engineering Science 205 (2019) 220–229
AOH group in the HEIBX molecule is deprotonated through
adsorption onto the chalcopyrite surface, and transformed into
the CAOACu moiety. In addition, the bands assigned to the C@S
stretching vibration group in the HEIBX molecule are weaker or
absent in the spectrum of the complex after adsorption onto the
chalcopyrite surface; the original peak at 1469 cm1 assigned to
the AC(@S)SA unit shifted to a higher frequency (1520 cm1) fol-
lowing adsorption, indicating that electrons had moved from the
C@S group to the Cu atom to form a CuAS bond on the chalcopyrite
surface (Liu et al., 2016). The FTIR data show that the AOH and C@S
groups are involved in the adsorption of HEIBX onto the chalcopy-
rite surface, which is consistent with the DFT results in Sec-
tion 3.2.1 that predicted that the AOH and C@S groups are the
reactive centers in HEIBX and can donate electrons to copper ions.
Fig. 10(b) reveals that the FTIR spectra of pyrite before and after
HEIBX treatment are almost identical, indicating a lack of obvious
chemical interaction between HEIBX and pyrite.
3.5.3. XPS measurements
The survey-scan XPS spectra of chalcopyrite samples in the 0–
1200 eV binding energy range are shown in Fig. S7, with the corre-
sponding element contents listed in Table S2. Treatment with
HEIBX clearly increases the carbon and oxygen contents, while
decreasing the sulfur, copper, and iron contents. The results are
consistent with the adsorption of HEIBX onto the chalcopyrite
surface.
In order to investigate the mechanism involved in the reaction
of chalcopyrite with the HEIBX molecule, high-resolution O 1s,
Cu 2p3/2, and S 2p3/2 spectra were acquired and are shown in
Fig. 11.
The O 1s peak of the original chalcopyrite sample is best fitted
by three peaks with energies of 529.75, 531.30, and 532.80 eV,
which correspond to O2 in oxide phases (Tan et al., 1990), OH
O 1s 531.30 eV
529.75 eV
532.80 eV
a a
Intensity
531.17 eV 531.90 eV
530.15 eV 533.14 eV
b
530 532 534
Binding Energy
y /eV
Cu 2p
a
Intensity
931.97 eV
b
930 931
Fig. 11. High-resolution O 1s, S2p, and Cu 2p XPS spectra (a untreated; b HEIBX-treated chalcopyrite).
227
of hydroxide species (Hirajima et al., 2017; Tan et al., 1990), and
the oxygen in sulfate or/and water (Ghahremaninezhad et al.,
2013), and indicates that the chalcopyrite was slightly oxidized.
The peak at 532.80 eV was absent after HEIBX adsorption, and
the band originally at 529.75 eV shifted to higher binding energy
(530.15 eV), which demonstrates that the electron density on the
chalcopyrite surface had changed. In addition, the peak at 531.30
eV could be deconvolved into two peaks at 531.17 and 531.90 eV;
the former peak is assigned to OH in hydroxide species, with the
latter corresponding to CuAOAC species (Farquhar et al., 2003;
Chen et al., 2012). Furthermore, a new peak was observed at
around 533.14 eV, which is assigned to the CAOAC unit in the
HEIBX molecule (Madec et al., 2015). These results indicate that
the AOH group in the HEIBX molecule had reacted to form
CAOACu bonds on the chalcopyrite surface, consistent with FTIR
results.
The S 2p3/2 spectrum of untreated chalcopyrite was resolved
into three peaks centered at 161.13, 162.02, and 163.25 eV, and
are assigned to metal sulfides (S2), metal-deficient disulfides
(S2 2
2 ), and polysulfides (Sn ), respectively (Hirajima et al., 2017;
Suyantara et al., 2018). The S 2p3/2 XPS spectrum of the chalcopy-
rite surface displayed three distinct peaks at approximately 161.09,
161.95, and 163.44 eV following HEIBX adsorption, which are
assigned to coordinated bulk S species (S2), and the Cu-S and C-
S-C units of Cu-HEIBX surface species (Farquhar et al., 2003; Liu
et al., 2011; Liu et al., 2017)). These results provide strong evidence
for the adsorption of HEIBX onto the chalcopyrite surface and the
formation of CASACu bonds, and further verifies the accuracy of
the DFT calculations and FTIR study that show that the S atoms
of the C@S groups donate their electrons to copper ions.
The Cu 2p3/2 spectrum was fitted using three peaks located at
931.96, 932.47, and 934.20 eV, assigned to CuFeS2, CuS and copper
(II) oxide/hydroxide species, respectively (Ma et al., 2017; Liu et al.,
S 2p 161.13 eV
162.02 eV
163.25 eV
Intensity
y
161.09 eV
161.95 e V
163.44 eV
b
160 162 164 166
Binding Energy /eV
931.96 eV
932.47
7 eV
934.20 eV
932.73 eV
932.97 eV
932 933 934 935 936
Binding Energy /eV
228 X. Huang et al. / Chemical Engineering Science 205 (2019) 220–229
Fig. 12. Proposed models for the adsorption of HEIBX onto the {1 1 2} chalcopyrite
surface ((I): HEIBX-Cu; (II): HEIBX-2Cu).
2015). The band at 934.20 eV was absent after the adsorption of
HEIBX, which indicates that HEIBX molecules are adsorbed onto
the chalcopyrite surface to cover copper species that were origi-
nally oxidized. Meanwhile, the band originally at 932.47 eV was
observed to shift by 0.26 eV to a value of 932.73 eV, indicating that
cupric ions are reduced to cuprous ions and Cu(I)AS bonds (Liu
et al., 2017; Lyu et al., 2018). Furthermore, a new peak was
observed at 932.97 eV, which is assigned to CuAOAC species that
originate from the reactions of copper species with the CAOH moi-
eties of HEIBX molecules (Ghahremaninezhad et al., 2013).
Based on the DFT calculations, FTIR spectroscopy, and XPS, we
conclude that HEIBX is adsorbed onto the chalcopyrite surface
through the formation of OACu and SACu bonds through reactions
involving its AOH and C@S groups. The oxygen atom (O11) and sul-
fur atom (S7) possibly anchor themselves to the same copper atom
on the chalcopyrite surface to form a seven-membered ring (I), or
they (O11 and S7) might simply interact with different copper
atoms on the chalcopyrite surface (II); the recommended proposed
adsorption models are presented in Fig. 12.
4. Conclusions
In this paper, we describe the preparation of HEIBX, a xanthate
derivative, through the attachment of a hydroxyethyl group to the
isobutyl xanthate ion and report its first use as a flotation collector
for the selective flotation-separation of chalcopyrite from pyrite;
its flotation performance was evaluated through the micro-
flotation experiments. DFT calculations, surface tension measure-
ments, and UV–vis spectroscopy were used to explore the flotation
performance of HEIBX. Contact angle measurements were used to
investigate the effect of HEIBX adsorption on the hydrophobicity of
the minerals. Zeta potentials were measured, and FTIR and XPS
spectra were acquired in order to further elucidate interactions
operating between the collector and the mineral. Based on the
experimental results, several conclusions are made.
DFT revealed that the functional sites of HEIBX are its C@S and
AOH groups, and that HEIBX is more chemically active and exhibits
a stronger electron-donating ability than the SIBX anion. Surface
tension measurements showed that attachment of the hydrox-
yethyl group to SIBX molecule increases its hydrophobicity and
enhances its arrangement density (amount adsorbed) on mineral
surface. In addition, HEIBX selectively interacts with chalcopyrite,
but not with pyrite, as confirmed by UV–vis spectroscopy.
Contact-angle experiments reveal that HEIBX selectively and
significantly improves the hydrophobicity of the chalcopyrite sur-
face, but has little effect on the pyrite surface. Micro-flotation
experiments further verify that HEIBX has a superior collecting
ability and selectivity for chalcopyrite over pyrite compared to
SIBX, with chalcopyrite/pyrite flotation-separation achieved using
4  105 molL1 HEIBX at pH 8.0.
Zeta potential experiments and FTIR spectroscopy reveal that
HEIBX is chemisorbed onto the chalcopyrite surface, while no obvi-
ous chemical interaction was observed between HEIBX and pyrite.
The XPS results suggest that HEIBX is adsorbed onto the chalcopy-
rite surface through the reactions of AOH and C@S groups and the
formation of O-Cu and SACu bonds on the surfaces.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
The authors gratefully acknowledge the National High Technol-
ogy Research and Development Program of China (863 Program,
Grant No. 2013AA064101) and National Natural Science Founda-
tion of China (Grant No. 21776320) for the financial support.
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ces.2019.04.051.
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