Journal of Cleaner Production 261 (2020) 121216

Contents lists available at ScienceDirect

Journal of Cleaner Production

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

Flotation of low-rank coal using sodium oleate and sodium

hexametaphosphate
Yijiang Li , Wencheng Xia *, Li Pan , Feng Tian , Yaoli Peng , Guangyuan Xie , Yanfeng Li
School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou, Jiangsu, 221116, China

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

Article history: A mixture of low-ash coal and gangue particles was used to investigate the effects of sodium oleate
Received 28 November 2019 (NaOL), kerosene, and sodium hexametaphosphate (SHMP) on low-rank coal flotation. X-ray photo-
Received in revised form electron spectroscopy etching revealed that NaOL was adsorbed on the coal surface effectively.
17 February 2020
Furthermore, zeta potential results confirmed the adsorption of NaOL and SHMP on the coal surface and
Accepted 18 March 2020
gangue surface. The yield of clean coal increased sharply with increasing NaOL dosage, while the clean
Available online 21 March 2020
coal ash content initially decreased with increasing NaOL dosage and then increased. Compared to the
Handling Editor: Zhen Leng use of kerosene alone, the addition of 3000 g/t sodium oleate can increase the yield of clean coal by about
50%. Compared to treatment without SHMP, the ash content of clean coal can be reduced by about 8%, the
Keywords: volatile matter and fixed carbon content clean coal can be increased by about 3% and 5% than using
Coal flotation 500 g/t SHMP. The fixed carbon content of clean coal decreased slightly with the SHMP dosage above
Sodium oleate 500 g/t. The contact angle results showed that NaOL enhanced the hydrophobicity of coal surface, while
Sodium hexametaphosphate SHMP did not significantly affect coal surface hydrophobicity. SHMP increased the electronegativities of
X-ray photoelectron spectroscopy etching
both coal and gangue, and enhanced the electrostatic repulsion between the coal and gangue particles.
Zeta potential
Scanning electron microscopy/energy-dispersive X-ray spectroscopy showed that the SHMP reduced the
amount of gangue particles coated on the coal surface, which reducing the ash content of clean coal. The
attachment time results showed that the coal particles adhered to the bubbles and agglomerated easily,
which greatly increasing the carrying capacity of single bubble to the froth layer and enhancing low-rank
coal flotation in the NaOL system. This study can recover combustibles from coal slime waste, which can
not only reduce the environmental pollution of slime, but also increase economic benefits.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction methods for combustion/reaction, and environmental friendly

Coal is a non-renewable fossil energy source that plays an
important role in the global energy supply. As the availability of
high-quality coal decreases, a lot of low-rank coal is being mined.
Globally, low-rank coal has become an important energy source
(Xia et al., 2015a,b). However, the presence of minerals, sulfur, and
heavy metals such as mercury severely limits the usage of coal as an
environmentally friendly fuel (Nyashina et al., 2018). If coal is not
separated before using, it will generate waste that pollutes the air,
water, and soil (Liu et al., 2019; Zhao et al., 2019). Thus, separating
low-rank coal before its utilization is essential.
At present, researches on the clean utilization of coal is mainly
focused on the separation of coal and gangue, clean and efficient
* Corresponding author.
E-mail address: xiawencheng@cumt.edu.cn (W. Xia).
treatment of coal waste (Chen et al., 2020; Dmitrienko et al., 2018;
Glushkov and Strizhak, 2017; Li et al., 2019a,b). Several economical
preparation technologies for coal separation, including crushing,
screening, gravity separation, and flotation, among others, have
been developed (Farrokhpay, 2011). Low-rank coal is easily broken
and slimed during the cleaning process due to its low meta-
morphosis, which usually results in raw coal slime with high ash
content. Coal slime, especially low-rank coal slime, is difficult to be
processed and utilized cleanly due to its high ash content, fine
particle size and complex surface properties. If the combustible
matter in fine coal slime is enriched or recovered by flotation, it will
not only reduce the air, water and soil pollution caused by coal
slime, but also save resources and increase the economic income
and employment of enterprises. Flotation is the most effective
approach for improving the grade of fine coal slimes. This method is
based on the difference in the surface hydrophobicity of coal and
gangue (Wen et al., 2017). However, the surface of low rank coal

https://doi.org/10.1016/j.jclepro.2020.121216
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
2 Y. Li et al. / Journal of Cleaner Production 261 (2020) 121216
contains many oxygen bearing functional groups, polar molecules
and pores/cracks, which complicating its flotation (Chen et al.,
2017; Wang et al., 2018). Conventional hydrocarbon oil does not
adsorb well on the surface of low-rank coal, and it cannot be used to
achieve highly effective bubble-particle adhesion. Therefore, the
development of highly effective collectors for low-rank coal has
become a vital issue.
Many researchers have investigated flotation reagents exten-
sively (Wen et al., 2017; Xia et al., 2015a,b). Dey (2012) reported
that surfactants with oxygen-bearing functional groups could
significantly enhance low-rank coal flotation. Li et al. (2019a,b)
found that soybean oil significantly enhanced coal flotation due
to its high content of fatty acids, which can adsorb on the surface of
anthracite and increase its flotability. Gui et al. (2017) reported that
the adsorption of a-furanacrylic acid on oxidized coal decreased its
zeta potential. Xia et al. (2015a,b) used a mixture of dodecane and
4-dodecylphenol to enhance lignite flotation. Jena et al. (2008) used
a collector called “black oil” to increase the flotability of oxidized
coal particles. The components of “black oil” have long carbon
chains and high content of functional groups such as CeO/OH/
COOH. These oxygen-containing collectors conspicuously improved
low-rank coal flotation performance (Dey, 2012; Tian et al.,
2017a,b). Sodium oleate (C17H33CO2Na, NaOL) is an inexpensive
and environmentally friendly anionic surfactant that used as the
collector and emulsifier for oxide ores flotation. Sodium hexame-
taphosphate ((NaPO3)6, SHMP) is widely used as an inhibitor or
dispersant in mineral flotation. Jue et al. (2015) demonstrated that
NaOL was adsorbed on an activated quartz surface at pH 12 using
quartz crystal microbalance and atomic force microscopy. Li et al.
(2011) found that the flotation of quartz in NaOL system was very
poor at pH < 11. Huang et al. (2017) found that oleate ions were not
well adsorbed on the quartz surface at pH 6e7. Wang et al. (2019)
observed that nanobubbles inhibited the adsorption of NaOL on
the calcite surface. In addition, Wang et al. (2014) found that SHMP
improved the hydrophilicity of coal and inhibited its floatation.
Furthermore, SHMP was found to reduce the adsorption of anionic
surfactant on the kaolinite surface (Choi et al., 1993).
In this paper, the effects of kerosene, NaOL, and SHMP on
flotation of low rank coal consisted of low-ash coal and gangue
particles were analyzed. X-ray photoelectron spectroscopy etching
(XPSE) technology was applied to reveal the influence of NaOL on
the coal surface. The effects of NaOL and SHMP on the hydropho-
bicity and electronegativity of the coal and gangue were investi-
gated using contact angle and zeta potential experiments. Scanning
electron microscopy/energy-dispersive X-ray spectroscopy (SEM/
EDS) was used to observe the effects of SHMP on the slime coating
on the coal surface. Attachment time tests were applied to analyze
the effects of NaOL on the adhesion of the coal/gangue particles to
bubbles.
2. Experimental materials and methods
2.1. Materials and reagents
Low-rank coal and gangue samples were obtained from the
Shanbula Coal Mine, Inner Mongolia, China. Firstly, 25e50 mm
lump coal and lump gangue were obtained from float-sink tests
using heavy fluids with densities of 1.3 g/cm3 and 1.8 g/cm3. Coal
(
1.3 g/cm3) and gangue (þ1.8 g/cm3) were crushed, ground, and
sieved to obtain
0.5 mm coal and gangue particles, respectively.
The proximate analyses of the low-ash coal, gangue, and flotation
feed sample are shown in Table 1. The coal and gangue were mixed
in a coal: gangue mass ratio (w/w) of 57:43, and the calculated ash
content of the flotation feed sample was 40.27%.
The results of the X-ray diffraction analyses of the gangue are
Table 1
Proximate analysis of low ash coal, gangue and the flotation feed sample.
Substance Mad (%) Aad (%) Vad (%) FCad (%)
Low-ash coal 7.74 6.45 37.71 48.10
Gangue 3.27 85.09 11.40 0.24
Flotation feed sample 5.82 40.27 26.40 27.52
Mad: moisture content on an air-dried basis. Aad: ash content on air-dried basis.
FCad: fixed carbon content on air-dry basis. Vad: volatile matter content on air-
dry basis.
shown in Fig. 1. The mineral present in the gangue was quartz
mainly and a little kaolinite. Table 2 lists the properties of the
kerosene, NaOL, SHMP and MIBC. In the experiments, the NaOL,
SHMP and MIBC were first dissolved in water. Deionized water used
with conductivity of 0.001 S/m and pH of 6.80 was used in the
experiments.
2.2. Flotation tests
2.2.1. Low-rank coal flotation using kerosene or/and NaOL
The flotation experiments were conducted in a 0.5 L micro-
flotation cell with the pulp mass ratio of 6% and the impeller
speed of 1900 rpm. Kerosene or/and NaOL were used as collector.
The collector dosage was 500, 1000, 2000, or 3000 g/t. Methyl
isobutyl methanol (MIBC) was added as frother at 70 g/t. The
experimental procedure was as follows. Firstly, the sample was pre-
wetted for 60 s, the kerosene or/and NaOL was then added, and the
pulp was stirred for 120 s. Then the frother was added, followed by
additional 30 s of stirring. Finally, the air flow of 250 ml/min was
introduced, and the clean coal was collected. The tailings were also
collected, and the yield, ash content, volatile matter content and
fixed carbon content of clean coal were calculated to compare the
flotation effects of different collector. The results are shown in
Table 3.
Before the effect of the SHMP dosage on coal flotation was
studied, the effect of the addition of kerosene and its dosage on coal
flotation at a constant NaOL dosage were determined. The results
are shown in Table 4. The best coal flotation results were obtained
when kerosene combined with NaOL.
2.2.2. Impact of SHMP on low-rank coal flotation
The flotation tests involving SHMP used nearly the same pro-
cedure as described in Section 2.2.1. The only difference with
respect to the above procedure was the addition of SHMP to the
pulp after initially stirring 60 s; the pulp was then stirred for
additional 120 s. To study the influence of SHMP on coal flotation,
SHMP dosages of 0, 500, 1000, 1500, and 2000 g/t were tested; the
Fig. 1. XRD analysis of gangue.
 Y. Li et al. / Journal of Cleaner Production 261 (2020) 121216 3

Table 2 The coal and gangue particles were ground into
0.074 mm
Reagents for low rank coal flotation. powder, which was then treated with different dosages of NaOL or
Regents Grade Molecular formula SHMP in the flotation pulp, and dried at 40  C. Finally, the treated
Kerosene Technical C9-16
powder was pressed into plates. Measurement of the coal and
NaOL Chemical C17H33CO2Na gangue plates was carried out using a contact angle analyzer. (JC
SHMP Analytical (NaPO3)6 2000D, Shanghai of China).
MIBC Technical C6H14O

2.4. SEM/EDS and zeta potential tests

Table 3 For SEM/EDS analysis, þ0.074 mm coal and
0.074 mm gangue

Effect of the kerosene and NaOL dosage on low-rank coal flotation.
were mixed in a 1:1 ratio. The mixture was conditioned with SHMP
Type of collector Dosage of collector (g/t) Clean coal in the flotation pulp; the pulp was then passed through the
Y/% Ad/% Vd/% FCd/% 0.074 mm sieve. Coal particles of >0.074 mm were dried and then
subjected to SEM analysis. After coating the samples with a layer of
Kerosene 500 2.72 27.52 30.67 41.81
1000 3.12 24.45 31.74 43.81
gold, a SIGMA 500 SEM (Carl Zeiss, Germany) was used to observe
2000 5.32 23.67 31.94 44.39 the slime coated on the coal surface at a magnification of 1000.
3000 5.52 19.42 33.28 47.30 Furthermore, EDS was used to determine the elemental composi-
NaOL 500 6.55 27.84 30.54 41.62 tion at selected points with the aim of observing the coating
1000 13.59 21.14 32.58 46.28
behavior of fine slime on the coal surfaces at different SHMP
2000 43.55 18.73 33.62 47.65
3000 57.15 22.70 32.11 45.19 dosages.
A Zeta plus PALS instrument (Brookhaven, USA) was used for the
Ad: ash content on dried basis. Vd: volatile matter content on dry basis. FCd: fixed
carbon content on dry basis.
measurement of the zeta potential of the coal and gangue particles.
The measurement procedure was as follows. Firstly, the coal and
gangue samples were ground to <2 mm using a laboratory grinding
Table 4 machine. Secondly, 50 mg of coal or gangue powder was wetted in a
Effect of kerosene on low-rank coal flotation at a fixed NaOL dosage. beaker with NaOL or SHMP aqueous solutions under different
Dosage of kerosene (g/t) Clean coal dosages. Thirdly, 5 min of ultrasound treatment was applied to
disperse the particles sufficiently. Finally, the suspension was
Y/% Ad/% Vd/% FCd/%
transferred to the zeta potential testing cell. In order to ensure the
500 60.10 25.95 30.86 43.19
accuracy of the results, the experiment was repeated three times
1000 62.79 24.53 31.80 43.67
2000 63.94 22.06 32.48 45.46
for each group, and the zeta potential was finally obtained as the
3000 63.30 20.28 33.86 45.86 average.

2.5. Attachment time tests

kerosene and NaOL dosages were kept constant at 3000 g/t and
2000 g/t coal, respectively. The results are presented in Table 5.
2.3. XPSE and contact angle tests
To observe the influence of NaOL on the low-rank coal surface,
XPSE technology was used to analyze the raw coal and the surface
and interior of the coal after treatment with NaOL. Firstly, the raw
coal was polished into block with a length and width of 5 mm and a
height of 2 mm. The coal block was then immersed in a 1% NaOL
solution for 10 min. To prevent the denaturation of NaOL, the coal
was then dried at 40  C for 1 h. Finally, XPSE analysis was
conducted.
The XPSE tests were carried out in an ultra-high vacuum (UHV)
surface analysis system (ESCALAB 250 Xi, USA) at room tempera-
ture. The surface of the coal was etched with an ion gun for cu-
mulative etching times of 5 s, 15 s, or 35 s, respectively. XPS peak
fitting software was applied to analyze the data.
The attachment time tests utilized the 0.074e0.5 mm coal and
gangue particles. Firstly, the coal and gangue particles were
immersed in the deionized water or NaOL aqueous solution cor-
responding to the dosage of 2000 g/t solid particles, and stirring for
5 min. The particles were transferred to the sample pool, where
they formed a highly suitable granular bed layer. An appropriate
volume of water or NaOL solution was then added. A bubble was
generated with a constant spacing between the bottom of the
bubble and the top of the particles bed. Adhesion between the
particles and the bubble was observed under a fixed contact time,
and 20 tests were performed to calculate the adhesion probability.
Due to the fact that the fine slime did not settle well in water, the
pulp was turbid, and it was difficult to observe the adhesion be-
tween the particles and bubble when SHMP was added. Therefore,
the attachment time was not investigated in the presence of fine
slime.
3. Results and discussion

3.1. Flotation results

Table 5
Effect of SHMP on low-rank coal flotation at the kerosene dosage of 3000 g/t and the
Table 3 indicates that the yield of clean coal does not increase
NaOL dosage of 2000 g/t.
significantly with increasing kerosene dosage; the highest yield is
Dosage of SHMP (g/t) Clean coal only 5.52% at the kerosene dosage of 3000 g/t. These results
Y/% Ad/% Vd/% FCd/% demonstrate that kerosene is not effective for the low rank coal
0 61.25 19.81 33.90 46.29 flotation. However, the yield of clean coal increased sharply with
500 61.31 11.31 36.16 52.53 increasing NaOL dosage. The yield of clean coal was only 6.55% at
1000 63.75 13.92 35.45 50.63 the NaOL dosage of 500 g/t, but increased to 57.15% at the NaOL
1500 63.91 12.50 35.83 51.67 dosage of 3000 g/t. Compared to kerosene, NaOL increased the yield
2000 63.91 13.13 35.62 51.25
of clean coal by about 50% at the dosage of 3000 g/t. Therefore,
4 Y. Li et al. / Journal of Cleaner Production 261 (2020) 121216

NaOL has a better collect effect in low-rank coal flotation than

kerosene.
Additionally, as the kerosene dosage increasing, the ash content
of clean coal gradually decreased to the minimum of 19.42%. The
clean coal ash content firstly decreased and then increased with
increasing NaOL dosage. At the NaOL dosage of 2000 g/t, the clean
coal ash content was 18.73%. With the increase of the dosage of
kerosene, the volatile matter content and fixed carbon content of
clean coal gradually increased. Compared with kerosene, the vol-
atile matter and fixed carbon content of clean coal treated by NaOL
are higher. These results showed that NaOL had better selectivity
than kerosene. This proved that clean coal produced by NaOL
flotation has higher organic matter content than that produced by
kerosene. The low rank coal have higher the volatile matter con-
tent, the more conducive to the coal chemical industry, and the
higher its economic value (Zhang, 2013).
Table 4 shows that when the dosage of NaOL is fixed at 2000 g/t,
the yield of clean coal increases with the kerosene dosage, while Fig. 2. Effect of the NaOL dosage on the contact angle of coal and gangue.
the ash content of clean coal gradually decreases. With the increase
of the dosage of kerosene, the volatile matter content and fixed
carbon content of clean coal gradually increased. These results the hydrophobicity of the coal surface. NaOL was selectively
demonstrate that the combined use of kerosene and NaOL is su- adsorbed on the surface of the coal particles, thus modifying the
perior to the use of NaOL or kerosene alone for low-rank coal coal surface more strongly than the gangue surface.
flotation. Fig. 3 shows that the hydrophobicity of the coal and gangue does
Table 5 shows that the yield of clean coal increases slightly with not change significantly with increasing SHMP dosage. The contact
increasing in SHMP dosage. The clean coal ash content decreased angle of coal was 44 e49 , and that of gangue was 14 e16 . Pre-
from 19.81% to 11.31% when the dosage of SHMP was increased vious research has shown that SHMP has a good dispersion effect
from 0 to 500 g/t. The volatile matter and fixed carbon content of on fine minerals (Jiang et al., 2012; Zhang et al., 2001). However, in
clean coal increased and then decreased with increasing of the this study, SHMP had little influence on the surface hydrophobicity
SHMP dosage. When the dosage of SHMP is 500 g/t, the content of of coal and gangue. Therefore, the impact of SHMP on the coal
volatile matter and fixed carbon is the highest. Both the yield and surface was not investigated using XPSE.
ash content of clean coal increased with increasing the SHMP Fig. 4 illustrates the C1s peak fitting for the raw coal and the
dosage from 500 to 2000 g/t, but the clean coal ash content was still NaOL-treated coal. Additionally, etching was used to evaluate the
much lower than 19.81%. These results showed that the dosage of chemical composition of the coal surface and interior by applying
SHMP had an obvious influence on the clean coal quality. SHMP is different ion etching times. For C1s, the peaks with binding en-
widely used as a dispersant in the mineral flotation. Jiang et al. ergies of 284.7 eV, 285.4 eV, 286.6 eV, and 288.5 eV were attributed
(2012) reported that SHMP adsorption enhanced the dispersion to CeC/CeH, C]C, C]O, and CeO groups respectively (Niu et al.,
of clay minerals in suspension, reducing their negative impact on 2017; Pietrzak et al., 2007).
coal flotation. Zhang et al. (2001) demonstrated that SHMP had an Fig. 4 and Table 7 demonstrate that the surface of NaOL-treated
impact on the zeta potential of gangue, increasing the dispersion of coal has higher C]O and CeO contents than the raw coal surface,
the coal slime and enhancing the flotation selectivity. In addition, and that these functional groups are derived from the oleate ions
the ultimate analysis of clean coal as shown in Table 6 revealed that adsorbed on the coal surface. The oleate ions on the coal surface
clean coal treated by kerosene, NaOL and SHMP has the low content after 5 s and 15 s of ion etching were then counted. As the interior of
of N and S, which is beneficial to the low rank coal applications in the coal sample was exposed, the C]C and CeO contents decreased
coal chemical industry and power production. A high content of C to 0, the CeC/CeH content increased, and the C]O content
and O, and low content of harmful elements help reduce the
environmental protection pressure of coal utilization. This study
confirmed that the SHMP can also be used as a dispersant in coal
flotation to disperse high-ash content fine slime from the coal
particle surface.

3.2 Contact angle and XPSE analysis

Fig. 2 illustrates the significant increase in the contact angle on

the coal from 44 to 60 with increasing NaOL dosage. The contact
angle of gangue increased slightly from 16 to 26 as the dosage of
NaOL was increased. This indicated that NaOL selectively enhanced

Table 6
Results of ultimate analyses of the clean coal at the kerosene dosage of 3000 g/t, the
NaOL dosage of 2000 g/t and the SHMP dosage of 500 g/t.

C O H N S

76.96 14.70 6.55 1.65 0.14

Fig. 3. Effect of the SHMP dosage on the contact angle of coal and gangue.
 Y. Li et al. / Journal of Cleaner Production 261 (2020) 121216 5

Fig. 4. Photoelectron spectra of (a) raw coal, (b) NaOL-treated coal surface, (c) coal surface after 5 s of etching, (d) coal surface after 15 s of etching.

Table 7 3.3. Zeta potential and SEM/EDS results

Functional groups composition of the coal surface before and after NaOL adsorption
and ion etching.
Fig. 6 shows that when the dosage of NaOL is increased from 0 to
Etching time CeC/CeH C¼C C¼O CeO 2000 g/t, the zeta potential of coal decreases from
19 mV to
54
Raw 63.68 28.57 5.66 2.09 mV, and then increases to
33 mV when the NaOL dosage is further
0s 63.68 23.11 7.33 5.88 raised to 3000 g/t. However, when the NaOL dosage was increased
5s 97.07 0 2.93 0 from 0 to 500 g/t, the zeta potential of the gangue decreased
15 s 97.65 0 2.35 0
from
8 mV to
17 mV. These results indicated that the application
of the proper dosage of NaOL can make the zeta potential of coal
particles more negative.
NaOL dissolves into oleate and Na þ ions in water. The oleate
decreased. Thus, the XPSE results proved that NaOL was adsorbed ions are strongly electronegative, and contain non-polar functional
on the coal surface. groups such as CeC/C]C and polar functional groups such as COO-.
Based on the XPSE and contact angle results, it was deduced that The adsorption of the polar functional groups reduced the zeta
the polar and non-polar ends of the oleate ions were adsorbed on potential of the coal surface. The non-polar functional groups were
the polar and non-polar regions of the coal surface, respectively. easily adsorbed on the non-polar regions on the coal surface. The
Many of the oxygen-bearing functional groups on the raw coal exposure of the carbon chains on the coal surface could enhance
surface may have been hydrogen-bonded to the oxygen-bearing the hydrophobicity of coal surface.
functional groups of the oleate ion. As shown in Fig. 5, side Fig. 7 shows that the zeta potential of coal decreases and then
chains consisting of CeC and C]C are exposed to the coal surface, increases with increasing SHMP dosage, reaching a minimum at
increasing the hydrophobicity of the coal particles. As a result, the 1000 g/t. Additionally, the zeta potential of gangue decreased and
attachment of the coal particles with oleate ions adsorbed on their then increased with increasing dosage of SHMP. The zeta potential
surface to the bubbles was easier than attachment of the raw coal to of coal was similar to that of gangue at the SHMP dosage of 500 g/t.
the bubbles. The electrostatic repulsion between the gangue particles and coal
6 Y. Li et al. / Journal of Cleaner Production 261 (2020) 121216
Fig. 5. Schematic of the interactions between the oleate ion (from NaOL) and the coal surface during flotation.
Fig. 6. Effect of the NaOL dosage on the zeta potential of the surfaces of the coal and
gangue particles.
Fig. 7. Effect of the SHMP dosage on the zeta potential of the surfaces of the coal and
gangue particles.
particles was the greatest at the SHMP dosage of 500 g/t. Hence, the
fine gangue slime on the coal surface could be effectively removed,
and reduce the high-ash fine slime into the froth. As a result, the
clean coal ash content was the lowest under these conditions, as
shown in the flotation results in Table 5.
As shown in Fig. 8, SHMP reduces the coating of fine slime on the
coal surface. Fig. 8(a) shows that a lot of fine gangue slime adhered
to the coal surface. These fine particles were analyzed using EDS
and found to primarily contain the elements K, Si, Al, Fe, and Ca,
whereas the main elements on the coal surface were C and O.
However, Fig. 8(b) shows that the main elements of both the fine
particle surface and the coal surface are C and O. These results
indicated that the fine particles attached to the coal surface at the
SHMP dosage of 500 g/t were primarily low-ash particles.
3.4. Attachment time analysis
Fig. 9(a) shows that the adhesion probability between the
bubble and the coal particles in the NaOL solution is 100% for
attachment times longer than 100 ms. In deionized water, the
probability of adhesion was less than 50% at 2000 ms. The decrease
in the attachment time indicated that NaOL had a positive influence
on the flotability/hydrophobicity of the coal particles. The influence
of NaOL on the adhesion probability between the gangue particles
and the bubble is shown in Fig. 9(b). The probability of the adhesion
of the gangue particles to the bubble was less than 10% even at the
contact time of 1000 ms in both pure water and NaOL solution. The
contact time was then increased to 10,000 ms; the adhesion
probability of gangue particles to the bubble in pure water was only
10%, while it was 30% in the NaOL solution. Compared to its effect
on the adhesion behavior between the coal particles and bubbles,
the enhancement of the adhesion of the gangue to the bubbles due
to NaOL was very small. Huang et al. (2017) reported that NaOL did
not adsorb on a quartz surface and did not change the hydropho-
bicity of quartz by fluorescent probe analysis. Therefore, NaOL has
little effect on the hydrophobicity of gangue particles, but selec-
tively enhances the flotability/hydrophobicity of coal particles.
Fig. 10 (a) illustrates the attachment of a single coal particle to
the bottom of the bubble in pure water, whereas Fig. 10 (b) illus-
trates the attachment of coal aggregates to the bottom of the bubble
in the NaOL system. These results demonstrate that the coal par-
ticles were readily agglomerated, which in turn greatly increases
the carrying capacity of a single bubble to the froth layer and en-
hances low rank coal flotation in the NaOL system. However, no
significant differences are observed between the gangue-bubble
attachment behavior of the pure water and NaOL system in
Fig. 10(c) and (d). This further indicated that NaOL selectively
enhanced the flotability/hydrophobicity of the coal particles, but
did not significantly affect the flotability/hydrophobicity of the
gangue particles.
 Y. Li et al. / Journal of Cleaner Production 261 (2020) 121216 7

Fig. 8. Effect of different SHMP dosages on the fine slime coating the coal surface: (a) 0 g/t, (b) 500 g/t.

Fig. 9. Effect of NaOL on the attachment time of (a) coal and (b) gangue.

4. Conclusion regions of coal surface, respectively, increasing the hydrophobicity/

flotability of coal. Compared to kerosene, NaOL can increase the
XPSE and contact angle results demonstrated that the polar and clean coal yield by about 50% at the dosage of 3000 g/t. Compared
non-polar ends of oleate ions adsorbed on the polar and non-polar to SHMP-free conditions, the ash content of clean coal can be
8 Y. Li et al. / Journal of Cleaner Production 261 (2020) 121216
Fig. 10. Adhesion between coal/gangue and bubbles in pure water and NaOL systems: a) Adhesion between coal and the bubble in pure water; b) adhesion between coal and the
bubble in the NaOL system; c) adhesion between gangue and the bubble in pure water; d) adhesion between gangue and the bubble in the NaOL system.
reduced by about 8% at the SHMP dosage of 500 g/t. Above this
value, the ash content of the clean coal increased slightly with
increasing SHMP dosage. The electrostatic repulsion between the
gangue particles and coal particles was greatest at the SHMP dosage
of 500 g/t, allowing the fine gangue slime on coal surface to be
effectively removed. The coal particles readily agglomerated in the
NaOL system, which greatly increased the carrying capacity of a
single bubble to the froth layer, and thus enhanced low-rank coal
flotation. NaOL selectively enhanced the flotability/hydrophobicity
of coal particles, but did not significantly affect the flotability/hy-
drophobicity of gangue particles. The combined use of NaOL,
kerosene, and SHMP in low-rank coal flotation will improve the
recovery efficiency of combustibles, reduce the impact of coal slime
on the environment, and provide economic benefits in industry.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
CRediT authorship contribution statement
Yijiang Li: Writing - original draft, Methodology, Software.
Wencheng Xia: Conceptualization, Supervision, Writing - review &
editing. Li Pan: Writing - review & editing. Feng Tian: Writing -
review & editing. Yaoli Peng: Writing - review & editing. Guan-
gyuan Xie: Writing - review & editing. Yanfeng Li: Writing - review
& editing.
Acknowledgements
The authors would like to thank the Advanced Analysis and
Computation Center of China University of Mining and Technology
for their technical support.
References
Chen, C., Zhao, L., Wu, X., Lin, S., 2020. Theoretical understanding of coal char
oxidation and gasification using reactive molecular dynamics simulation. Fuel
260, 116300.
Chen, S., Yang, Z., Chen, L., Tao, X., Tang, L., He, H., 2017. Wetting thermodynamics of
low rank coal and attachment in flotation. Fuel 207, 214e225.
Choi, I.K., Wen, W.W., Smith, R.W., 1993. The effect of a long chain phosphate on the
adsorption of collectors on kaolinite. Miner. Eng. 6, 1191e1197.
Dey, S., 2012. Enhancement in hydrophobicity of low rank coal by surfactants-A
critical overview. Fuel Process. Technol. 94, 151e158.
Dmitrienko, M.A., Nyashina, G.S., Strizhak, P.A., 2018. Major gas emissions from
combustion of slurry fuels based on coal, coal waste, and coal derivatives.
J. Clean. Prod. 177, 284e301.
Farrokhpay, S., 2011. The significance of froth stability in mineral flotation-A review.
Adv Colloid Interfac 166, 1e7.
Glushkov, D.O., Strizhak, P.A., 2017. Ignition of composite liquid fuel droplets based
on coal and oil processing waste by heated air flow. J. Clean. Prod. 165,
1445e1461.
Gui, X., Xing, Y., Wang, T., Cao, Y., Miao, Z., Xu, M., 2017. Intensification mechanism
of oxidized coal flotation by using oxygen-containing collector a-furanacrylic
acid. Powder Technol. 305, 109e116.
Huang, Y., Wang, W., Zheng, K., Wang, Y., Feng, Q., Yang, Q., 2017. Flotation behavior
and mechanism of andalusite and quartz in the presence of sodium oleate. Min.
Metall. Eng. 37, 61e65.
Jena, M.S., Biswal, S.K., Rudramuniyappa, M.V., 2008. Study on flotation character-
istics of oxidised Indian high ash sub-bituminous coal. Int. J. Miner. Process. 87,
42e50.
Jiang, S., Kai, Z., Pei, J., Liu, J., 2012. Inhibition mechanism and application of Sodium
Hexametaphosphate to coal slime. China Coal 38 (4), 83e85.
Jue, K., Yu, G., Tichang, S., Shihong, X., Chengyan, X., 2015. Adsorption mechanism of
two different anionic collectors on quartz surface. J. Cent. S. Univ. 46,
4005e4014.
Li, L., Yin, W., Feng, D., Xue, S., Zhang, B., 2011. Floatability performance of iron
minerals and quartz in system of sodium oleate. Metal. Mine 40 (8), 68e71.
Li, Y., Xia, W., Hu, Z., Peng, Y., Xie, G., 2019a. Filling of nanocarbon particles in the
pores of unburned carbon and its application in gasification ash separation. ACS
Omega 4, 18787e18792.
Li, Y., Xia, W., Zhang, N., 2019. Efficiency and mechanism analysis of the flotation of
anthracite coal using soybean oil as an alternative sustainable collector. Energy
Sources, Part A: Recovery, Utilization, and Environmental Effects. https://
doi.org/10.1080/15567036.2019.1644400.
Liu, X., Bai, Z., Shi, H., Zhou, W., Liu, X., 2019. Heavy metal pollution of soils from coal
mines in China. Nat. Hazards 99, 1163e1177.
Niu, C., Xia, W., Xie, G., 2017. Effect of low-temperature pyrolysis on surface prop-
erties of sub-bituminous coal sample and its relationship to flotation response.
Fuel 208, 469e475.
 Y. Li et al. / Journal of Cleaner Production 261 (2020) 121216
Nyashina, G.S., Kuznetsov, G.V., Strizhak, P.A., 2018. Energy efficiency and envi-
ronmental aspects of the combustion of coal-water slurries with and without
petrochemicals. J. Clean. Prod. 172, 1730e1738.
Pietrzak, R., Grzybek, T., Wachowska, H., 2007. XPS study of pyrite-free coals sub-
jected to different oxidizing agents. Fuel 86, 2616e2624.
Tian, Q., Wang, Y., Li, G., 2017a. Application of special collectors and flotation col-
umn for beneficiation low rank coal slimes. Physicochem. Probl. Mi. 53,
553e568.
Tian, Q., Zhang, Y., Li, G., Wang, Y., 2017b. Application of carboxylic acid in low-rank
coal flotation. Int. J. Coal Prep. Util. 1e10.
Wang, L., Ma, L., Yu, Y., 2014. Application and mechanism study of sodium hex-
ametaphosphate in coal flotation. Coal Technol. 33, 203e205.
Wang, S., Guo, J., Tang, L., He, H., Tao, X., 2018. Effect of surface roughness of Chinese
sub-bituminous coal on the kinetics of three-phase contact formation. Fuel 216,
531e537.
9
Wang, Y., Pan, Z., Luo, X., Qin, W., Jiao, F., 2019. Effect of nanobubbles on adsorption
of sodium oleate on calcite surface. Miner. Eng. 133, 127e137.
Wen, B., Xia, W., Sokolovic, J.M., 2017. Recent advances in effective collectors for
enhancing the flotation of low rank/oxidized coals. Powder Technol. 319, 1e11.
Xia, W., Ni, C., Xie, G., 2015a. Effective flotation of lignite using a mixture of
dodecane and 4-dodecylphenol (DDP) as collector. Coal Prep. 36, 262e271.
Xia, W., Xie, G., Peng, Y., 2015b. Recent advances in beneficiation for low rank coals.
Powder Technol. 277, 206e221.
Zhang, G.F., Feng, Q.M., Lu, Y.P., Liu, G.Y., Ou, L.M., 2001. Effect of sodium hexame-
taphosphate on flotation of bauxite. J. Cent. S. Univ. Technol. 32 (2), 127e130.
Zhang, S., 2013. Coal Chemistry. Chemical Industry Press Co.,Ltd, Beijing, China.
Zhao, Z., Wang, R., Ge, L., Wu, J., Yin, Q., Wang, C., 2019. Energy utilization of coal-
coking wastes via coal slurry preparation: the characteristics of slurrying,
combustion, and pollutant emission. Energy 168, 609e618.