Journal of Cleaner Production xxx (2016) 1e16

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Journal of Cleaner Production

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Clean low-rank-coal purification technique combining cyclonic-static

microbubble flotation column with collector emulsification
Yaowen Xing a, Xiahui Gui b, *, Yijun Cao b, Dapeng Wang b, Haijun Zhang b
a
School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou 221116, Jiangsu, China
b
Chinese National Engineering Research Center of Coal Preparation and Purification, China University of Mining and Technology, Xuzhou 221116, Jiangsu,
China

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

Article history: The flotation upgrading of low-rank-coal is more difficult to achieve than that of bituminous and/or
Received 29 May 2015 anthracite coal, especially for micro-fine coal slime, because of developed porosity and a large number of
Received in revised form oxygen surface functional groups and low collision probability between bubble and particle. In this
8 November 2016
paper, previous works on high-efficiency low-rank-coal flotation were reviewed first and a clean micro-
Accepted 9 November 2016
Available online xxx
fine low-rank-coal purification technique that innovatively combined a cyclonic-static microbubble
flotation column with collector emulsification was proposed. The results show that a satisfactory sepa-
ration performance for micro-fine low-rank-coal flotation can be obtained by using a cyclonic-static
Keywords:
Low-rank-coal
microbubble flotation column with collector emulsification. The collision probability between a coal
Purification particle and diesel increased because of the collector emulsification. The specific adsorption of the
Cyclonic-static micro-bubble flotation surfactant on the hydrophilic groups on the particle surface also increased the hydrophobicity. The
column improved micro-fine low-rank-coal flotation performance by cyclonic-static microbubble flotation col-
Collector emulsification umn can be attributed to the high collision probability because of turbulent mineralization mechanism
and micro-bubbles, and high attachment probability and low detachment probability because of the
introduction of the hydrophobic attractive force due to the existence of the nanobubble. The outcome of
this research provided a new insight into the flotation of low-rank-coal and other difficult-to-float coal.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction coal provides energy supply security and guarantees economy-

Coal is the main fossil fuel in many countries, accounting for
almost 70% of the primary energy consumption especially in China
(Lin et al., 2010; Dang, 2012). The reserves distribution data of coal
resources in China is shown in Table 1 (Liu et al., 2014). The
Ascertain reserve is as high as 1341.20 billion tones. Although ad-
justments have been made to adjust the energy structure and
renewable energy utilization techniques have been developed in
recent years, coal is expected to occupy a dominant position in the
energy structure for a long time because coal-based energy is
determined by the “rich coal, lack of gas and oil” situation in China
(Niu et al., 2005; Liu, 2011). According to China's sustainable energy
development strategy, the proportion of coal in the energy con-
sumption structure will still account for 50%, and the demand will
not reduce below 2 billion tons of standard coal by 2050. Therefore,
* Corresponding author.
E-mail address: guixiahui1985@163.com (X. Gui).
society development in China.
However, coal is not a clean source of energy. Coal-fired power
generation is the main reason for the worsening air pollution levels
(Johnson et al., 2008; Andric et al., 2015; Mao et al., 2014). Ash
content distribution of commercial coal for power generation in
China is show in Table 2 (Liu et al., 2014). It indicates that the
average ash content of commercial coal for power generation is as
high as 23.85%. The global problem of energy insecurity and climate
change has given rise to the new concept of “low-carbon” usage. A
low-carbon economy is an economic model based on low energy
consumption, pollution, and emission. Aimed at efficient energy
utilization and clean energy development as well as the pursuit of a
green gross domestic product, the core of a low-carbon economy is
to promote social development by relying on technological prog-
ress (Du and Liu, 2011; Dou, 2013; Chang, 2015). China has the
largest energy consumption and carbon emission levels in the
world because of its coal-dominated energy structure. Coal con-
sumption percentage statistics in different industries in China is
shown in Table 3 (Liu et al., 2014). Many difficulties exist in

http://dx.doi.org/10.1016/j.jclepro.2016.11.057
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Please cite this article in press as: Xing, Y., et al., Clean low-rank-coal purification technique combining cyclonic-static microbubble flotation
column with collector emulsification, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.11.057
2 Y. Xing et al. / Journal of Cleaner Production xxx (2016) 1e16

Table 1 has aroused immense concern for the wellbeing of the entire so-
The reserves distribution of coal resources in China (billion tons
101). ciety. Fog and haze have negative effects on the respiratory tract of
Province Numbers of mining area Basic reserves Ascertain reserves the human body because they can be absorbed through the lungs
Beijing 28 3.79 19.32
and may cause acute upper respiratory infection, acute tracheal
Tianjin 2 2.97 3.82 bronchitis, and pneumonia, as well as induce or aggravate chronic
Hebei 249 60.59 167.45 bronchitis, especially in children, who have soft bronchial mucosa
Shanxi 609 844.01 2673.79 and fewer alveoli than adults. These problems are also increasingly
Neimenggu 527 796.86 3577.45
prevalent in India, Russia, and other developing countries. Because
Liaoning 487 46.63 79.25
Jilin 447 12.40 26.17 of pressure arising from natural resource shortages and the
Heilongjiang 238 68.17 217.83 increasing threat of unsuitable air quality, the Chinese government
Jiangsu 127 14.23 36.01 made a commitment at the 2009 Copenhagen World Climate
Zhejiang 68 0.49 0.94
Conference to reduce carbon dioxide emissions in the country by
Anhui 221 81.93 299.58
Fujian 242 4.06 10.29
40%e45% by 2020 from the levels recorded in 2005. Clean and high-
Jiangxi 174 6.74 15.02 efficiency utilization of coal resources and effective control of
Shandong 303 77.56 253.25 greenhouse gas emissions are major issues to be solved with
Henan 315 113.49 179.74 China's rapid economic development.
Hubei 288 3.30 7.91
In conclusion, the development of alternative clean energy and
Hunan 624 18.76 32.19
Guangdong 188 1.89 6.30 the adjustment and optimization of the coal-dominated energy
Guangxi 180 7.74 22.36 structure are necessary for the sustainable development of society.
Hainan 8 0.90 1.67 Finding a reliable method to improve clean coal utilization is the
Chongqing 370 22.49 40.05 key to control the current haze problem in China.
Sichuan 621 54.45 117.76
Guizhou 985 120.29 593.62
Coal preparation processing and upgrading is the most eco-
Yunnan 405 62.47 295.33 nomic and effective method to achieve clean coal utilization (Chen,
Xizang 23 0.12 0.56 2012). Mineral impurities in coal, which are the main factors
Shanxi 216 119.89 1654.23 causing environmental pollution, affect the efficiency of coal
Gansu 220 58.05 150.68
burning. Because of poor coal quality, high ash content, and a single
Qinghai 91 16.22 48.01
Ningxia 107 54.03 348.09 product structure, the problems of low-efficiency coal utilization
Xinjiang 491 148.31 2433.31 and serious environmental pollution are further highlighted in
Total 8854 2795.83 13,411.98 China. However, organic matter and inorganic minerals can be
separated effectively by coal preparation processing and upgrading
(e.g., gravity separation and flotation). Consequently, pollution due
achieving a low-carbon economy. According to big data statistics, to coal burning is inhibited because ash and sulfur content in raw
the pollution caused by burning coal in China accounts for 70% of coal is considerably reduced. According to big data statistics, the
the total dust emissions, 85% of the total sulfur dioxide emissions, coal separation process can remove more than 60% of ash content
67% of the total nitrogen oxide emissions, and 80% of the total and 50%e70% of pyrite sulfur content (Wang et al., 2004). If 100
carbon dioxide emissions (Liu, 2011). The resulting environmental million tons of raw coal is separated before burning, SO2 emissions
and human health problems have been externalized on the Chinese can be reduced by 1.0 million tons to 1.5 million tons. If the ash
society during recent decades because of a narrow focus on rapid content of coal used for power generation is decreased by 1%,
economic development (Wong, 2013). Smog problems represented standard coal consumption can be reduced by 2e5 g per kilowatt of
by particulate matter 2.5 (PM2.5) have particularly become power generated. As a result, the total CO2 emissions per year can
increasingly prominent in most Chinese provinces; this increase be reduced by approximately 15 million tons to 37.5 million tons in

Table 2
Ash content distribution of commercial coal for power generation in China.

Area Average ash (%) Percentage(%)

Ultra-low ash Low ash Middle-low ash Middle ash High-middle ash High ash

North China 20.85 0.14 4.40 49.54 33.73 11.19 0.99

Northeast 27.15 0.00 2.25 29.72 27.78 29.31 10.94
East China 26.64 0.00 0.39 18.93 53.09 23.48 4.11
South Central 26.15 0.05 0.04 21.75 60.39 6.76 11.02
Southwest 27.56 0.00 0.34 10.88 56.58 30.26 1.94
Northwest 16.84 5.74 9.03 62.17 17.59 5.47 0.00
Total 23.85 0.48 2.74 34.95 40.70 16.60 4.53

Table 3
Coal consumption percentage statistics in different industries in China.

Industries 1995 2000 2005 2006 2007 2008 2009

Agriculture and forestry 1.35% 1.25% 1.07% 0.97% 0.56% 0.54% 0.53%
Industry 85.40% 90.38% 93.49% 94.28% 93.93% 94.48% 94.61%
Construction industry 0.32% 0.41% 0.28% 0.24% 0.23% 0.21% 0.21%
Transportation 0.96% 0.86% 0.38% 0.30% 0.27% 0.24% 0.22%
Accommodation and catering industry 0.71% 0.62% 0.40% 0.37% 0.68% 0.64% 0.67%
Living consumption 9.83% 5.99% 4.03% 3.51% 3.58% 3.25% 3.08%
Others 1.44% 0.50% 0.35% 0.33% 0.75% 0.64% 0.67%

Please cite this article in press as: Xing, Y., et al., Clean low-rank-coal purification technique combining cyclonic-static microbubble flotation
column with collector emulsification, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.11.057
 Y. Xing et al. / Journal of Cleaner Production xxx (2016) 1e16 3

Table 4
The development of coal wash industry in China.

Year 2000 2005 2006 2007 2008 2009 2010 2011 2012

Raw coal production (billion tons
101) 12.99 22.05 23.73 25.26 27.88 29.73 32.40 35.20 36.60
Volume of washed (billion tons
101) 3.37 7.03 7.80 11.00 12.50 14.00 16.50 18.70 20.50
Wash rate (%) 25.90 31.90 32.90 43.50 44.80 47.10 50.90 53.00 56.00

the entire country (Liu, 2011). To date, significant developments in Table 6

coal and coal preparation industry were achieved in China. The The distribution of coal types in China.

development of coal wash industry in China is shown in Table 4 Coal Type Percent (%)
(Gui et al., 2015). The quantity and raw coal wash rate in China Anthracite 11.60
have increased since 2000. The volume of prepared coal increased Meagre coal 6.00
from 730 million tons in 2005 to 2.05 billion tons in 2012; the ratio Weakly caking coal 1.80
of prepared raw coal increased from 31.9% to 56.00%. It should be Non-caking coal 15.80
Long flame coal 14.70
noted that the raw coal wash rate is still lower than that of devel-
Lignite 12.80
oped country, as shown in Table 5. The “National Energy and Long- Gas coal and 1/3 coking coal 13.10
term Development Plan (2004e2020)” states that energy has a Fat coal 3.80
particularly important strategic position in the national economy. Coking coal 6.48
Lean coal 4.22
Measures such as promoting clean utilization of coal, reducing
Cokeite 0.20
environmental pollution, and striving to develop clean coal tech- Others 9.50
nology must be promoted. Therefore, the preparation and purifi- Total 100
cation of coal have become strategic initiatives for the harmonious
development of environment and energy. In China, clean coal
technology and processing began in the 1950s. The first production Table 7
line for coking coal preparation by desulfurization and deashing The reserves distribution of brown coal in China.
was established in the 1960s. Since the implementation of reforms Province Reserves (%)
and the Open Door Policy in China, the coal preparation industry
Inner Mongolia 77.1
has seen considerable progress in terms of production quantity,
Yunnan 12.6
wash rate of raw coal, and methods and equipment used. China's Heilongjiang 2.6
advanced coal preparation technology can be implemented at large Liaoning 1.5
industry scales and at a high level of control compared with those Shandong 1.3
of other countries. Jilin 0.9
Guangxi 0.8
The beneficiation process of low-rank-coals is more difficult to Others 3.2
achieve than that of bituminous and/or anthracite coals, especially Total 100
for micro-fine coal slime. Nearly half of the coal resources in the
world are low-rank-coal (Sivrikaya, 2014). China is known to be
abundant in low-rank-coal, but the rate of its utilization is quite most effective method for fine coal upgrading. However, a low
low. According to big data statistics, the low-rank-coal account for yield, developed porosity, and a large number of oxygen surface
68.42% of the whole resources in China, as shown in Table 6. Lignite functional groups in fine low-rank-coal lead to low separation ef-
resources with high moisture and high ash content account for 13% ficiency and necessitate the use of highly oily collectors (Jia et al.,
(130 billion tons) of the proven reserves, mainly in Inner Mongolia, 2000; Yu et al., 2013). Achieving a satisfactory yield or combus-
northeast provinces, and Yunnan Province. The reserves distribu- tible recovery as well as ash content is difficult with the imple-
tion of brown coal in China is shown in Table 7. In addition, long- mentation of conventional froth flotation methods. The upgrading
flame coal, non-caking coal, weak-caking coal, and other low- of industrial fine low-rank-coal through flotation has been reported
rank-coal account for 35% of the proven reserves (Song, 2013). To to be barely successful in China. To maximize coal production and
date, initially washed low-rank-coal is generally used for thermal utilization, coal mining operations and preparation have been
power generators and in the coal chemical industry. Coarse sepa- highly mechanized, which produces high proportions of micro-fine
ration based on density and fine fractions without separation are low-rank-coal. If these fine fractions are directly incorporated into
frequently used in coal power plants. With the development of final concentrates without washing, product quality would be
gravity beneficiation technology, the separation efficiency of coarse degraded and subsequent contamination during coal combustion
particles by heavy medium separation is considered to be better would increase. Therefore, developing a low-cost, high-efficiency
than that by flotation (Falcon and Ham, 1988). Froth flotation is the micro-fine low-rank-coal flotation technology is greatly necessary.
In addition, the green separation of low-rank-coal is an important
Table 5 strategic choice to achieve guaranteed energy security and an
Statistics of coal wash rate in the world. environment for sustainable development in the country.
Country Coal wash rate (%)

The United States 55.00 2. Review of previous work on low-rank-coal flotation

Russia 60.00
Germany 95.00
Poland 40.00 Froth flotation is an effective separation method for fine-coal
Australian 75.00 cleaning based on the differences between the surface hydropho-
South Africa 60.00 bicity of organic matter and mineral matter (Tao et al., 2002; Jena
Canada 95.00 et al., 2008; Barraza et al., 2013). Hydrophobic particles are sepa-
China 50.90
rated by allowing them to attach to rising air bubbles that form a

Please cite this article in press as: Xing, Y., et al., Clean low-rank-coal purification technique combining cyclonic-static microbubble flotation
column with collector emulsification, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.11.057
4 Y. Xing et al. / Journal of Cleaner Production xxx (2016) 1e16
Fig. 1. The schematic of froth flotation (Nguyen, 2013).
particle-rich froth on the suspension surface. The schematic of froth
flotation is shown in Fig. 1 (Nguyen, 2013). However, the floatability
difference between low-rank-coal particles, which has developed
porosity and a large number of oxygen surface functional groups,
and gangue is minimal. The thinning rate of the thin liquid film
between a bubble and particle is slow, preventing bubbleeparticle
adhesion (Pan et al., 2011, 2012). To improve the flotation efficiency
of low-rank-coal, considerable successful explorations have been
conducted by researchers. The objective of following section is to
highlight the effect of different intensification methods like particle
surface modification, particle surface pretreatment, bubble surface
modification and high efficiency flotation equipment, on the
flotation of fine low-rank-coal.
2.1. Particle surface modification
Low-rank-coal flotation can be intensified by suitable particle
surface modification technology. The addition of oily collectors
(kerosene and diesel) is the most common method for coal particle
surface modification. However, satisfactory flotation of low-rank-
coal is difficult to achieve by using common oily collectors
because of its low surface hydrophobicity (Xing et al., 2017; Gui
et al., 2017). Cebeci (2002) found that the combined addition of
kerosene, an emulsifier, and a surfactant in the low-rank-coal
flotation process could produce clean coal with low ash content
and high combustible recovery. The surface hydrophobicity could
be increased through surfactant adsorption on the coal surface and
through hydrogen bonding. The pore penetration tendency was
also reduced with the use of surfactants because of the increase in
viscosity. Simultaneously, emulsification could considerably
decrease the amount of collector dosage. Jia et al. (2002) used a
series of non-ionic surfactants, containing oxygenated and aro-
matic functional groups, i.e., tetrahydrofurfuryl esters (THF), as
collectors to enhance low-rank/oxidized-coal flotation. The mem-
bers of the THF series were found to be more effective collectors
than the oily collectors for both oxidized and unoxidized coals. The
attachment mechanism of the THF series of reagents on the coal
surface is shown in Fig. 2. The reagents appear to function through
hydrogen bonding with surface-oxygenated sites on the coal sur-
face and hydrophobic bonding of the hydrocarbon chain of the
collector with hydrophobic carbonaceous sites on the coal surface.
If the coal surface is highly aromatic, a benzene ring in the collector
chain will considerably improve the effectiveness of the collector to
carry out flotation because of the interaction of the benzene ring
with aromatic groups on the coal surface. Li (2014) studied the use
of condensate diesel as the collector for low-rank-coal flotation.
Higher flotation recovery and separation index than those afforded
by conventional diesel were obtained. The Fourier transform
infrared (FTIR) analysis of conventional diesel and condensate
Please cite this article in press as: Xing, Y., et al., Clean low-rank-coal purification technique combining cyclonic-static microbubble flotation
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Fig. 2. The attachment mechanism of the THF series of reagents on the coal surface
(the affinity of individual functional group of reagents for the coal surface is repre-
sented as in the diagram) (Jia et al., 2002).
diesel are shown in Fig. 3. In the spectrum of condensate diesel, a
peak can be found at 1714 cm1, whereas in the spectrum of con-
ventional diesel, no such peak is observed. The absorbent peak
classifications of the FTIR spectrum of condensate diesel are listed
in Table 8. The results indicate that more oxygen groups (1714 cm1,
C¼O) exist in condensate diesel because of the oxidation reaction
occurring in the high-temperature condensation process of con-
ventional diesel. The presence of these oxygen-containing com-
pounds considerably improves the hydrophobicity of the coal
surface by hydrogen bonding. Moxon et al. (1987) studied the rival
effects of pore penetration and surface spreading on the collector
efficiency of straight chain hydrocarbons (with chain lengths of
C6eC16) during coal froth flotation. The maximum flotation yield
was obtained for a hydrocarbon chain length of C12. The flotation
yield of hydrocarbons with shorter chain lengths was retarded by
the penetration of liquids into the coal pores, which effectively
reduced surface concentration. The yield of hydrocarbons with
longer chain lengths (>C12) was also retarded by viscosity effects,
which effectively reduced the rate of surface spreading of the liquid
over the coal surface. These results indicated that hydrocarbons
with long chain lengths are highly suitable for low-rank-coal
flotation because of their developed porosity. Xia et al. (2013a)
found that biodiesel containing abundant unsaturated fatty acids
was better at improving the flotation of oxidized coal than con-
ventional diesel. Atesok and Celik (2000) observed a distinct in-
crease in flotation recoveries when pitch was added in dry grinding,
followed by the flotation of a low-rank-coal in the presence of
typical collectors. The high separation efficiency was attributed to
better penetration and selective attachment of high-molecular-
weight components of the high-viscosity pitch onto the hydro-
phobic groups on the coal surface.
2.2. Particle surface pretreatment
Low-rank-coal flotation can also be enhanced by different
 Y. Xing et al. / Journal of Cleaner Production xxx (2016) 1e16 5

Fig. 3. The FTIR analysis of conventional diesel (A) and condensate diesel (B) (Li, 2014).

pretreatment methods such as ultrasonic, microwave, and thermal poor hydrophobicity similar to that of low-rank-coal. The flotation
methods. Feng and Aldrich (2005) used two preconditioning rate and recovery obtained with ultrasonic preconditioning were
methodsdultrasonication and high-intensity conditioning (HIC)d higher than those obtained with HIC. Both the thin clay layer and
in an agitated vessel to improve the flotation of oxidized coal with oxidation layer were removed from the coal surface by ultrasound

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6 Y. Xing et al. / Journal of Cleaner Production xxx (2016) 1e16

Table 8
Classification of absorbent peak of FTIR spectrum of condensate diesel
(Li, 2014).

Wavenumbers,cm1 Function groups

3447 eOH
2975e2880 CeH
1714 C]O
1634 C]C
1459,1377 eCH2e, eCH3
744 Benzene

pretreatment. Meanwhile, ultrasonic preconditioning created the

most stable froth, giving the smallest bubbles and the highest de-
gree of mineralization. Ozkan (2012) found that ultrasonic coal
flotation yielded higher combustible recovery and lower ash con-
tent in concentrates than conventional flotation for similar reagent
dosages. The increase in recovery was attributed to better surface
cleaning effects and increased efficiencies of favorable collision,
attachment, and detachment because of ultrasonically generated
cavitation. The mechanism of ultrasonically generated cavitation
bubbles in coal flotation is shown in Fig. 4. Cavitation bubbles can
replace clay particles in the flotation process. Oezbayoglu et al.
(2009) and Xia et al. (2013b) studied the effect of microwaves on
low-rank/oxidized-coal flotation. The floatability of coal particles
was restored because of the removal of moisture content and
dehydration by microwave pretreatment. Celik and Seyhan (1995)
also studied the effects of heat treatments in improving the sur-
face hydrophobicity of lignite. Heat treatment decreased the
negative zeta potential values of low-rank-coals and reduced the
intensity peaks of hydrophilic groups. Zhang et al. (2013a) similarly
found that hydrothermal treatment could increase the hydropho-
bicity and floatability of low-rank-coal because of the removal of
considerable oxygen-containing groups. Fig. 5 shows the FTIR Fig. 5. FTIR spectra of the lignite sample before and after different temperature
spectra of the lignite sample before and after different temperature heating treatments: (a) at ambient temperature and (b) at 105  C for 4 h (Cinar, 2009).
heating treatments. The peaks of oxygen-containing functional
groups can be seen to be considerably weakened.
carrier in flotation. The comparison of conventional flotation and
reactive oily bubble flotation is shown schematically in Fig. 6. Oily
2.3. Bubble surface modification bubbles attain a much higher contact angle than air bubbles,
generating a strong collecting power, which is suitable for the
The characteristics of bubbles, which act as transportation car- flotation of both coarse and fine particles. Su et al. (2006) subse-
riers of particles in flotation, have an important effect on separation quently demonstrated that oily bubbles could improve bitumen
performance. Low-rank-coal flotation can also be enhanced by recovery from poor processing ores by increasing the spread of
suitable bubble surface modification technology. Liu et al. (2002) three-phase contact lines in preliminary laboratory tests, this
proposed a novel concept of using reactive oily bubbles as a improvement was reflected by the reduced induction time required

Fig. 4. The mechanism of ultrasonically created cavitation bubbles in coal flotation Fig. 6. The comparison of conventional flotation (a) and reactive oily bubble flotation
(Ozkan, 2012). (b) (Liu et al., 2002).

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 Y. Xing et al. / Journal of Cleaner Production xxx (2016) 1e16 7

for attaching air bubbles to bitumen surfaces. Wang et al. (2011)
first used oil bubbles to enhance the flotation recovery of low-
rank-coal. A higher flotation rate and recovery, better separation
selectivity, and lower reagent consumption than those in conven-
tional bubble flotation were obtained. A prototype technology
based on oil bubbles was proposed for low-rank/oxidized-coal
flotation. Recently, nanobubble application to laboratory columns
has proven to be very successful for hard-to-float fine coal (Sobhy
and Tao, 2013; Tao et al., 2008). The specially designed nano-
bubble flotation column featuring a hydrodynamic cavitation
nanobubble generator is shown in Fig. 7. This design not only
considerably improved combustible recovery but also reduced re-
agent and air consumption because nanobubbles increased the
probabilities of collision and attachment and decreased the prob-
ability of detachment.
2.4. High efficiency flotation equipment
Flotation equipment is another important parameter affecting
flotation performance (Polat et al., 2003; Gupta et al., 2009). In
addition to the characteristic of low contact angle, developed
porosity and a large number of oxygen functional groups on low-
rank-coal surface, the problem of micro-fine particle are also
acute because of the easily slimezation property of low-rank-coal.
0.125 mme0.074 mm size fraction is the optimal size range for
fine coal flotation. For particles smaller than 74 mm, the recovery
drops rapidly with reducing particle size. From the perspective of
flotation kinetics, the recovery of micro-fine particle is dominant by
the collision probability. Micro-fine particles are strongly influ-
enced by viscous drag. Such particles tend to follow the streamlines
when particles approach the bubble, resulting in a low collision
probability. It is well accepted that micro-fine particle flotation
recovery can compensate by reducing the bubble size and
increasing the shear rate in the environment surrounding the
bubbles in the flotation cell. For conventional flotation machine, the
turbulence environment is not high enough to achieve effective
bubble-particle collision. On the other hand, the diameter of bub-
bles in flotation machine was usually in the range of 1e3 mm and it
is too big for micro-fine particle flotation. As a result, slow flotation
rate and low recovery were obtained by using conventional flota-
tion machine for micro-fine particle flotation. Tao et al. (2002) re-
ported that the Ken-Flote-type flotation column was inferior to
mechanical flotation equipment for oxidized coal, which has poor
natural floatability similar to that of low-rank-coal. Tao claimed
that the conclusions may only be applied to Ken-Flote-type flota-
tion columns with quiescent flow condition. For a flotation column
that using the turbulent collection mechanism, such as the Jameson
cell, the results may be close to or even better than those of a
mechanical flotation machine. Therefore, Han et al. (2014) used a
coal flotation column developed by Canadian Process Technologies
(CPT), which provides highly turbulent mineralization for low-
rank-coal flotation. The performance and separation efficiency of

Fig. 7. The specially designed nanobubble flotation column featuring a hydrodynamic cavitation nanobubble generator (Sobhy and Tao, 2013).

Please cite this article in press as: Xing, Y., et al., Clean low-rank-coal purification technique combining cyclonic-static microbubble flotation
column with collector emulsification, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.11.057
8 Y. Xing et al. / Journal of Cleaner Production xxx (2016) 1e16
the column were far superior to that of the conventional cell. The
comparison of combustible recovery, ash rejection and separation
efficiency for CPT column and conventional flotation is shown in
Fig. 8. For the CPT flotation column, an acceptable clean coal
concentrate with 85% combustible recovery and 81% ash rejection
was obtained, whereas for the conventional cell, the concentrate
had only 70% combustible recovery and 70% ash rejection. A highly
turbulent mineralization mechanism is considerably important for
micro-fine low-rank-coal flotation. The cyclonic-static microbubble
Fig. 8. The comparison of combustible recovery, ash rejection and separation effi-
ciency for CPT column and conventional flotation (Han et al., 2014).
Fig. 9. The schematic of the cyclonic-static micro-bubble flotation column (Zhang et al., 2013a, b).
Please cite this article in press as: Xing, Y., et al., Clean low-rank-coal purification technique combining cyclonic-static microbubble flotation
column with collector emulsification, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.11.057
flotation column (FCSMC) is also a high efficiency flotation equip-
ment for micro-fine low-rank-coal flotation. The schematic of the
FCSMC is shown in Fig. 9. The FCSMC consists of a flotation column,
cyclone separation zone, and pipe flow zone. Countercurrent
mineralization was applied to generate high-quality concentrate
from the raw materials. Cyclone mineralization in the cyclone
separation step, which incorporated density separation and surface
flotation, further separated the flotation middling to obtain high-
quality tailings. The pipe flow mineralization zone was connected
perpendicularly to the cyclone separation zone in the tangential
direction with high Reynolds numbers. An external bubble gener-
ator based on the principle of a venture cavitation sparger was
installed in the pipe flow mineralization zone to take in and crush
air into microbubbles, which can promote ultrafine particle flota-
tion performance. Moreover, nanobubbles, which are favor to
flotation of difficult-to-float coal because of the introduction of the
hydrophobic force, were produced on the coal particle surfaces by
the hydrodynamic cavitation effect. Pulp continuously flowed be-
tween the cyclone separation zone and the pipe flow zone through
a circulation pump (Zhang et al., 2013b; Xing et al., 2015). In
summary, the FCSMC followed three mineralization pat-
ternsdcountercurrent collision mineralization, cyclone minerali-
zation, and pipe flow mineralization to achieve a perfect
mineralization reaction mechanism and separation process.
FCSMCs have been widely used in the separation of ultrafine coal,
metal (nickel, copper, iron, gold, aluminum, molybdenum, and lead
and zinc), and non-metallic minerals (phosphorus and fluorite)
because of their superior separation selectivity.
As seen from the literature review, the difficulty of the micro-
fine low-rank-coal flotation is attributed to the low hydrophobici-
ty and collision probability. High-efficiency flotation of micro-fine
low-rank-coal has attracted the attention of many researchers.
The methods proposed above by researchers could obtain a better
separation performance compared with that of traditional flotation.
However, most of these studies are still in the laboratory stage
because the actual applications of the proposed methods are hin-
dered by some disadvantages such as the high energy consumption
 Y. Xing et al. / Journal of Cleaner Production xxx (2016) 1e16 9

of ultrasonic, microwave, and thermal pretreatment on particle
surface and the high oil consumption and security problems of oily
bubble production using the method of bubble surface modifica-
tion. The universality of the collectors for surface modification re-
mains a challenge and high efficiency flotation equipment with
turbulent collection mechanism may be limited by high detach-
ment probability for coarse low-rank-coal. Many improvements are
still required for the industrial application of low-rank-coal flota-
tion. Among the numerous enhancement methods available, col-
lector emulsification and the use of a flotation machine with highly
turbulent mineralization and nanobubble formation show better
performance for micro-fine low-rank-coal flotation than the other
methods because of their high efficiency and practicability. Col-
lector emulsification can improve the low-rank-coal flotation per-
formance through increased the collision probability between a
coal particle and diesel particle and attachment probability be-
tween coal particle and bubbles. Also the surface hydrophobicity
increased through surfactant adsorption on the coal surface and
through hydrogen bonding. In the FCSMC, the pipe flow minerali-
zation zone can create a more favorable fluid condition for micro-
fine particleebubble collision because of high Reynolds numbers
condition and micro-bubbles. Furthermore, the creation of the
nanobubble is favor to flotation of difficult-to-float coal because of
the introduction of the hydrophobic force. So, it is necessary to
explore the separation performance of the micro-fine low-rank-
coal flotation using FCSMC. However, the combination of a highly
turbulent flotation machine and collector emulsification was rarely
reported. The theoretical analysis of the mechanism is still lacking
and further studies are needed. The present study aims to develop a
low-cost, high-efficiency micro-fine low-rank-coal purification
processing technology which is of significant practical and aca-
demic importance for difficult-to-float coal flotation. Based on
previous analyses, this paper proposes to innovatively combine the
use of a FCSMC with collector emulsification. The separation per-
formance is then compared with that of a conventional mechanical
flotation process and the intensification mechanism of FCSMC
combined with collector emulsification is also discussed in detail
from the perspective of flotation kinetics. The outcome of this
research will increase flotation efficiency and provide a new insight
into the micro-fine low-rank-coal flotation.
3. Experimental materials and procedure
Low-rank-coal samples were collected from a mine in Inner
Mongolia, China. The elemental composition analysis and proxi-
mate analysis of coal samples were performed using the vario
MACRO cube (Elementar, Germany) and an industrial analyzer, and
the results are listed in Tables 9 and 10. Angle analysis was per-
formed using an optical contact angle measurement instrument
(DSA100, Germany). The contact angle of the coal samples was
41.1, which indicates good hydrophilicity.
The wet screening test of the coal samples was performed using
a set of standard sieves (0.500, 0.250, 0.125, 0.074, and 0.045 mm).
The particle size and ash content distributions are presented in
Table 11. The ash content gradually increased with the increasing
particle size. The major size fractions were 0.045 mm, the yield
was 78.48%, and the ash content was 29.85%. These micro-fine
fractions with high ash content can easily degrade concentrates
by mechanical entrainment during the flotation process.
A GL-21 M high-speed centrifuge, with a centrifuge speed of
3000 rpm, was used for density analysis. The specification of the
centrifuge tube was 4
250 ml; that is, four centrifuge tubes with
volumes of 250 ml were arranged symmetrically in the centrifuge.
The centrifugal liquid was an organic solution prepared by mixing
carbon tetrachloride, benzene, and tribromethane. This procedure
was also described in another study (Gui et al., 2013). The density
analysis data of samples are listed in Table 12. The major density
fractions were in the range of 1.4e1.5 g/cm3, the yield was 48.26%,
and the ash content was 13.96%. A large number of intergrowth
materials which were non-liberated particles formed by gangue
minerals and coals were identified. In the theoretical analyses, an
ash content of 15.24% and a yield of 75.99% were obtained at a
separation density of 1.6 g/cm3.
The procedure used for the emulsified diesel preparation is
described as follows. First, three surfactants (i.e., Span80, Tween80,
and triethanolamineoleate) were mixed in a mass proportion of
36:48:16, and the mixture was used as the emulsifier. The oile-
water ratio in the mass fraction was 3:7. Second, 3% emulsifier was
added into the oilewater mixture and subjected to high-speed
mixing (3000 rpm) using a homogenate machine for 5 min.
Finally, qualified emulsified diesel was obtained by carrying out
ultrasonic dispersion treatment at 53 Hz frequency for 3 min.
An XFDIII 0.75 dm3 laboratory flotation machine was used in the
conventional flotation tests. Firstly, the required amount of water
was added into the flotation cell to prevent the dry coal particles
sticking to the bottom and walls of the cell. Then the impeller speed
was kept constant at 1800 rpm and 45 g coal samples were poured
into the cell. This operation (prewetting process) was performed
over a period of 2 min. After the prewetting process, common diesel
collector and an octanol frother were added step by step into the
pulp. The collector and frother conditioning periods were 2 and
1 min, respectively. At the end of conditioning period, bubbles
induced by agitator passed through the pulp forming froth on the
upper pulp surface. The air flow rate was kept constant at 2.5 dm3/
min. The flotation process was maintained for 3 min. The froth
products and tailings were dried and weighed for ash analysis,
respectively.
After initial testing using a batch flotation cell combined with
emulsification to determine the optimal flotation conditions, tests
were performed by combining the FCSMC with emulsification. The
flotation column equipment used in this experiment was a
laboratory-scale FCSMC (diameter: 50 mm, height: 2000 mm)
invented by our team leader, Liu (1999).
Coal was mixed with emulsified diesel and octanol in a mixed
tank for 5 min, and the resulting coal slurry was fed to the FCSMC

Table 9
Element compositions of the coal sample. Table 11
Constituent C H O N S Size analysis data of the samples.

Percentage, % 74.7 5.13 17.96 1.39 0.82 Size, mm Mass fraction,% Ash,% Oversize Undersize

Yield,% Ash,% Yield,% Ash,%

þ0.25 1.04 13.42 1.04 13.42 100.00 27.47

Table 10 0.25e0.125 1.30 12.54 2.34 12.93 98.96 27.62
Proximate analysis of the coal sample (ad: air dried basis, daf: dry ash-free basis). 0.125e0.074 7.87 13.26 10.21 13.18 97.66 27.82
0.074e0.045 11.31 23.87 21.52 18.80 89.79 29.10
Constituent Moisture (ad) Ash (ad) Volatile matter(daf) Fixed carbon(daf)
0.045 78.48 29.85 100.00 27.47 78.48 29.85
Percentage, % 10.07 25.12 47.48 52.52 Total 100.00 27.47

Please cite this article in press as: Xing, Y., et al., Clean low-rank-coal purification technique combining cyclonic-static microbubble flotation
column with collector emulsification, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.11.057
10 Y. Xing et al. / Journal of Cleaner Production xxx (2016) 1e16

Table 12
Density analysis data of the samples.

Density fractions,g/cm3 Yield,% Ash content,% Cumulative of floating Cumulative of sediments

objects

Yield,% Ash,% Yield,% Ash,%

1.3 1.91 5.32 1.91 5.32 100 27.60

1.3e1.4 8.66 6.24 10.57 6.07 98.09 28.03
1.4e1.5 48.26 13.96 58.83 12.54 89.43 30.14
1.5e1.6 17.16 24.49 75.99 15.24 41.17 49.11
1.6e1.7 18.4 66.25 94.39 25.18 24.01 66.71
þ1.7 5.61 68.23 100 27.60 5.61 68.23
Total 100 27.60

using a pump. The feed inlet was located at a distance equivalent to

one-third of the column height from the top. The FCSMC operating
conditions, unless noted otherwise, were as follows: 0.1 Mpa
circulating pressure, 60 g/dm3 solid content, 1.33 dm3/min feed
rate, 2.5 dm3/min air flow rate, 0.8 dm3/min wash water flow rate,
and 0.3 m froth height. A pump was used to discharge the flotation
tailings. A time period equivalent to that required for three particle
retentions was allowed to achieve steady-state conditions. The
concentrate and tailing products were then collected for ash
analysis.
The combustible recovery and faultless index, which were used
to evaluate the performance of flotation, were calculated by using
Eqs. (1)e(3).

Adf  Adt
Yield ð%Þ ¼
100 (1)
Adc  Adt

100  Adc
Combustible recovery ð%Þ ¼ Yield

100
100  Adt
Yield Adf  Adc
Faultless index ð%Þ ¼

100
100  Adf Adf
where Adf, Adc, and Adt are the ash contents of the feedings,
concentrate, and tailings, respectively.
4. Results and discussion
Conventional mechanical flotation experiments were per-
formed with and without emulsified diesel. Flotation of FCSMC
combined with emulsified diesel was also conducted and the
intensification mechanism of cyclonic-static microbubble flotation
column combined with collector emulsification was discussed
briefly. The results and discussion are presented below.
4.1. Conventional mechanical flotation with and without emulsified
diesel
The effect of common diesel dosage on conventional flotation
performance is shown in Fig. 10. The dosage of the frother was kept
constant at 0.20 kg/t. The results indicate that the consumption of
common diesel dosage without emulsification was maintained at a
high level (30e80 kg/t). As the dosage of the collector increased, the
combustible recovery and ash content increased. However, the
faultless index increased initially and then decreased slightly. This
was because of the large number of mineral matter floating in the
froth products with excessive diesel dosage. The optimal separation
performanced16.79% ash content, 74.27% combustible recovery,
and 35.09% faultless indexdwas obtained at a common diesel
consumption of 60 kg/t. The effect of emulsified diesel dosage on
(2)
Fig. 10. The effect of common diesel dosage on conventional flotation performance.
(3)
conventional flotation performance is shown in Fig. 11. As the
dosage of emulsified diesel increased from 5 to 10 kg/t, the
combustible recovery, ash content, and faultless index also
increased. For a collector dosage of more than 10 kg/t, the
combustible recovery increased slightly and the faultless index
decreased. The optimal separation performanced17.65% ash con-
tent, 81.53% combustible recovery, and 34.98% faultless indexdwas
obtained at an emulsified diesel consumption of 10 kg/t. Clearly,
diesel emulsification can considerably reduce collector dosage
(60e10 kg/t) while giving similar separation results.
To identify the intensification mechanism of the emulsified
diesel on coal flotation, the contact angles and Zeta potential of the
coal surface with and without emulsified diesel were conducted. 45
g coal samples were added into an XFDIII 0.75 dm3 flotation ma-
chine. Common diesel with dosage of 10 kg/t and emulsified diesel
with dosage of 10 kg/t were added into the pulp conditioning for
15 min, respectively. Then, the pulp was filtered, dried and pressed
for contact angle measurement. Results show that the contact an-
gles of the coal surface with common diesel and emulsified diesel
were 43.6 and 53.1, respectively. It indicates that the contact
angle slightly increased compared with that of raw coal (41.1 )
when 10 kg/t common diesel was added into the pulp. However, the
result was different for emulsified diesel of equal dosage. The
contact angle increased to 53.1 considerably. In the collector
emulsification process, the interfacial tension between diesel and
water was reduced by the addition of the surfactant, which resulted
in a uniform and stable dispersion of diesel oil in water at a smaller
particle size. Consequently, the collision probability between a coal
particle and diesel particle increased which leading to the
increasing of contact angle and reduction of collector consumption.

Please cite this article in press as: Xing, Y., et al., Clean low-rank-coal purification technique combining cyclonic-static microbubble flotation
column with collector emulsification, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.11.057
 Y. Xing et al. / Journal of Cleaner Production xxx (2016) 1e16 11

Fig. 11. The effect of emulsified diesel dosage on conventional flotation performance. Fig. 12. The effect of frother dosage on conventional flotation performance with
emulsification.

It should be noted that the increasing of contact angle is also

probably due to the specific adsorption of the surfactant on the
hydrophilic groups on the particle surface. The polar head group of
the surfactant was readily anchored to the hydrophilic groups of
coal particles, while the hydrocarbon chains exposed to the solu-
tion rendering the coal surface more hydrophobic (Xie, 2009;
Zhang et al., 2015). The Zeta potentials of coal suspensions were
measured with a Zeta PALS instrument (Brookhaven Instruments
Co., New York). A suspension with 0.1 wt% coal particles
(0.074 mm) was prepared in an ultrasonic bath in 1 mM KCl so-
lution containing 10 kg/t common diesel or emulsified diesel. The
upper portion of dilute fine particle suspension was taken after 24 h
settlement for Zeta potential measurement. Each measurement
was repeated five times at room temperature (25 ± 1  C) and the
average value was reported. The Zeta potentials of raw coal, coal
particles with common diesel, and coal particles with emulsified
diesel were 50.41, 47.32, and 29.58 mV, respectively. The raw
coal exhibit a high negative because of abundant oxygen groups on
low-rank-coal surface. The Zeta potential significantly increased
to 29.58 mV when emulsified diesel was added, while potential of
coal particles with common diesel almost identical to that of raw
Fig. 13. The effect of impeller speed on conventional flotation performance with
coal. It illustrates that the surfactant adsorbed on the negative emulsification.
charged coal surface made the zeta potentials less negative. As a
result, the electrostatic repulsion between coal and bubble
decreased and bubble-particle attachment was enhanced. respectively. The combustible recovery and faultless index
To determine the optimal separation performance of mechanical increased initially and then decreased as the impeller speed
flotation with emulsified diesel, the effects of the frother dosage increased. In addition, the ash content decreased initially and then
and impeller speed on low-rank-coal flotation were investigated. increased. This is due to the difficulty of maintaining the suspended
The effect of frother dosage (0.14, 0.18, 0.20, 0.24, and 0.28 kg/t) on status of the coal particles in the pulp with a very low energy input.
conventional flotation performance with emulsification is shown in The low combustible recovery and faultless index were attributed
Fig. 12. The dosage of emulsified diesel was kept constant at 10 kg/t. to the low collision probability among the bubble, particle, and
The flotation recovery increased slightly, where as ash content diesel. A small impeller speed may result in particle aggregation in
increased considerably with increasing frother dosage. Therefore, the flotation pulp with a reduction in the flotation selectivity
actual flotation processes should probably be carried out because of the entrapment of ash materials in the agglomerated
completely at a low frother dosage. Increasing the frother dosage structure. When the rotor speed was too high, the froth stability
may lead to high entrainment of minerals and ash recovery. The was completely disturbed, the probability of detachment increased,
optimal faultless index (36.26%) was obtained at a frother con- and the combustible recovery and faultless index decreased. Water
sumption of 0.18 kg/t. Notably, collector emulsification can slightly entrainment also increased as the impeller speed increased, leading
reduce frother dosage. This phenomenon is partly attributable to to high ash recovery. The optimal separation performance was
the foaming property of the surfactant in emulsified diesel. obtained at an impeller speed of 2000 rpm.
The effect of impeller speed on conventional flotation perfor- In conclusion, the optimal flotation performance of mechanical
mance with emulsification is presented in Fig. 13. The dosages of flotation with emulsified dieseld17.22% ash content, 83.41%
emulsified diesel and the frother were 10 and 0.18 kg/t, combustible recovery, and 36.55% faultless indexdwas obtained

Please cite this article in press as: Xing, Y., et al., Clean low-rank-coal purification technique combining cyclonic-static microbubble flotation
column with collector emulsification, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.11.057
12 Y. Xing et al. / Journal of Cleaner Production xxx (2016) 1e16

when 10 kg/t of diesel and 0.18 kg/t of the frother were used at an first-order flotation rate constant k can be expressed as (Yoon and
impeller speed of 2000 rpm. However, diesel consumption was Mao, 1996):
high compared with that in coking coal flotation. Therefore, the
industrial application of emulsion flotation for micro-fine low- 1
k ¼ Sb P (4)
rank-coal will not have economic benefits. 4

where Sb is the bubble surface area flux. Sb is related to the su-

4.2. Flotation of FCSMC combined with emulsified diesel perficial gas velocity Jg by the relationship (Han et al., 2014):

The coal sample has a large number of micro-fine fractions, as Jg

Sb ¼ 6 (5)
listed in Table 11. Micro-fine particle flotation, especially in the case Db
of conventional flotation, frequently encounters the problems of
low recovery, poor selectivity, and high reagent consumption. where Db is the diameter of the bubble, Jg is defined as the volu-
Compared with the conventional flotation machine, the pipe flow metric air rate divided by the cross-sectional area of column.
mineralization zone can create a more favorable fluid condition for The collection efficiency P in Eq. (4) is the consequence of three
micro-fine particleebubble collision because of high Reynolds sub-processes, namely collision, attachment and detachment in the
numbers condition and micro-bubbles. In this section, a clean low- overall collection process. It indicates that an ultimate success of
rank-coal purification technique that combines the use of the the flotation process depends on the capture of particles of interest
FCSMC with collector emulsification is presented. The effect of by bubbles in the pulp phase and the successful transfer of the
emulsified collector dosage on FCSMC performance is shown in aggregate to the froth phase (Ahmed and Jameson, 1989).
Fig. 14. The optimal flotation performance of the FCSMC with
emulsified dieseld17.33% ash content, 90.85% combustible recov- P ¼ Pc Pa ð1  Pd Þ (6)
ery, and 40.79% faultless indexdwas obtained when 6 kg/t of diesel
and 0.18 kg/t of the frother were used. A comparison of the optimal where Pc is the probability of bubbleeparticle collision, Pa is the
flotation performances of the conventional flotation machine and probability of bubbleeparticle attachment, and Pd the probability of
FCSMC is presented in Table 13. For similar ash content concen- bubbleeparticle detachment.
trates, the FCSMC not only effectively reduced the collector con- A simple derivation of the mathematical expression k is shown
sumption but also provided a better separation performance. This is as follows (Yoon and Mao, 1996):
mainly because of the highly turbulent mineralization mechanism
 2
in the FCSMC, which created a more favorable condition for micro- 3 4Re0:72 Dp
Pc ¼ þ (7)
fine particleebubble collision and oil absorption on the coal sur- 2 15 Db
face. From the perspective of flotation kinetics, it is well established
 
that the flotation can be described as a first-order process and the E
Pa ¼ exp  1 (8)
Ek

" 2
#
4E1 þ pglv D2p ð1  cos qÞ
Pd ¼ exp  (9)
4Ek0

Substituting Eqs. (5)e(9) into Eq. (4):

    ( "
3 Jg 3 4Re0:72 Dp 2 E1
k¼ þ exp 
1  exp
2 Db 2 15 Db Ek
#)
4E1 þ pglv D2p ð1  cos qÞ2
 (10)
4Ek0

where Dp is the diameter of the particle, Re is the Reynolds number

Fig. 14. The effect of emulsified collector dosage on FCSMC performance.
of the bubble, E1 is energy barrier for bubble-particle attachment,
Ek is the kinetic energy of a particle approaching a bubble, glv is the
surface free energy at liquid/vapor interface, q is the contact angle,
Ek0 is the kinetic energy that tears the particles off the bubble
surface.
As shown by Eqs. (4e10) above, the collision probability Pc de-
creases with the decreasing of the particle diameter. For micro-fine

Table 13
The comparison of the optimal flotation performance of conventional flotation and FCSMC.

Flotation method Octanol dosage, Collector dosage, Concentrate Concentrate Tailings Tailings Combustible Faultless
kg/t kg/t ash,% yield,% ash,% yield,% recovery,% index,%

Flotation cell without 0.20 60.00 16.79 64.99 47.59 35.01 74.27 35.09
emulsification
Flotation cell with 0.18 10.00 17.22 73.06 53.90 26.94 83.41 36.55
emulsification
FCSMC with emulsification 0.18 6.00 17.33 79.61 67.50 20.39 90.85 40.79

Please cite this article in press as: Xing, Y., et al., Clean low-rank-coal purification technique combining cyclonic-static microbubble flotation
column with collector emulsification, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.11.057
 Y. Xing et al. / Journal of Cleaner Production xxx (2016) 1e16 13

Fig. 15. Bubble size distribution in FCSMC under 0.1 Mpa circulating pressure.

particles, they were strongly affected by viscous drag but not by which has been proven to enhance flotation. Zhou et al. (1997)
inertia. Considering the diverge when particles approaching the found that nanobubbles preferentially nucleated on hydrophobic
bubble, fine particles tended to follow the streamline, which surfaces selectively without collision, which was conducive to
leading to a low collision probability. It should be noted that the micro-fine particle flotation. Additional, nanobubbles on the hy-
flotation constant k vary approximately as D3 b and Re
0.72
, which drophobic surface of micro-fine particles can lead to particle ag-
suggests that one of the effective methods enhancing the miero- gregation because of attractive capillary force interactions when
fine particle flotation is the using of small air bubbles and high two surfaces come into contact (Hampton and Nguyen, 2010).
turbulent environment. In the FCSMC, the Reynolds numbers of the After bubbleeparticle collision, the attachment process
bubble and particle in the pipe flow mineralization zone were occurred, which was found to be controlled by the surface force
maintained at a high level. Fluid in the space was characterized by
high-frequency pulsing. A large-scale vortex was rapidly split into
small-scale vortexes by viscous shear force. As a result, a large
bubble was sheared by a small eddy into smaller bubbles (micro-
bubbles), which increased the collision probability. The bubble size
in FCSMC under 0.1 Mpa circulating pressure have been measured
by our team using a high-speed camera system. The results are
show in Fig. 15. More than 80% bubbles diameter are smaller than
1 mm. It indicates that the diameter of bubble in FCSMC is much
smaller than that of conventional flotation machine (1e3 mm). The
high turbulent mineralization mechanism in pipe zone of FCSMC is
shown in Fig. 16 (Yan, 2013). Meanwhile, high-frequency pulsing
effectively prevented the tendency of micro-fine particles to follow
the streamlines. A relative velocity difference between the fluid and
particles was produced. The collision probability among the bubble,
particle, and reagents increased further. Under a high-speed jet
condition, a secondary mechanical emulsification effect of the Fig. 17. The steps of the rupture process of the wetting film in detail using gas bubbles
agents may occur and cause a decrease in the amount of emulsified adhered to a solid substrate (A) for a large film thickness hw, where no rupture occurs,
diesel. Another benefit of the FCSMC was the nanobubble genera- nanobubble play no roles in film behavior (B) Film rupture occurs at a film thickness on
the order of the biggest bubble height (hw ¼ hrupture) (Stockelhuber et al., 2004).
tion by hydrodynamic cavitation (Hampton and Nguyen, 2010),

Fig. 16. The high turbulent mineralization mechanism in pipe zone of FCSMC (Yan, 2013).

Please cite this article in press as: Xing, Y., et al., Clean low-rank-coal purification technique combining cyclonic-static microbubble flotation
column with collector emulsification, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.11.057
14 Y. Xing et al. / Journal of Cleaner Production xxx (2016) 1e16

(Pan et al., 2012). It is well established that bubbleeparticle
attachment probability Pa also increases with decreasing bubble
size Db (Yoon and Luttrell, 1989), indicating micro-bubbles are
conducive to flotation. However, the classical Derja-
guineLandaueVerweyeOverbeek theory often fails to predict the
behavior of aqueous films involving hydrophobic solid surfaces
and/or airewater interfaces. In present study, a force named the
hydrophobic force was critically important for the attachment of
particles to air bubbles in the flotation process. A number of re-
searchers have claimed that the mechanism of the hydrophobic
attractive force originates from the bridging of pre-existing
nanobubbles on the hydrophobic surface (Nguyen et al., 2003; Peng
et al., 2015). Therefore, the thinning rupture of a thin liquid film
(i.e., wetting film) between a bubble and particle was dominated by
the hydrophobic attractive force and nanobubbles. Stockelhuber
et al. (2004) studied the steps of the rupture process of the wet-
ting film in detail using gas bubbles adhered to a solid substrate, as
shown in Fig. 17. For films whose thickness hw was greater than the
bubble height hb, nanobubbles were deduced to have no role in the
rupture process (Fig. 17(a)). As hw was adjusted according to hb,
interaction hydrophobic forces were stimulated between the film
surface and the largest nanobubble (Fig. 17(b)). Film rupture and

Fig. 18. AFM image of a nanobubble that exists on a hydrophobic surface with a contact angle of 165 (Johnson et al., 2012).

Fig. 19. The effect of a nanobubble on an enlarged contact angle (Ahmadi et al., 2014).

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 Y. Xing et al. / Journal of Cleaner Production xxx (2016) 1e16
attachment hen occurred. From the Eq. (8), bubbleeparticle
attachment probability Pa increases with the decreasing of energy
barrier E1 for bubble-particle attachment. Obviously, E1 would
decrease because of the introduction of the hydrophobic attractive
force due to the existence of the nanobubble.
Furthermore, after collision and attachment sub-processes,
particle-bubble aggregates transported to the froth phase and
some of them detached from bubble surface and drop back into the
pulp phase. As shown in Eq. (9), good hydrophobicity and high
contact angle meaning a low bubbleeparticle detachment proba-
bility and high flotation rate constant. Atomic force microscopy
(AFM) studies have shown that the contact angle of a nanobubble
on the hydrophobic surface is much larger than the macroscopic
contact angle (Borkent et al., 2010; Johnson et al., 2012). For
example, on the same hydrophobic surface, AFM analysis mea-
surements gave a macroscopic contact angle of 72.61 and a
nanoscopic contact angle of 165 . AFM image of a nanobubble that
exists on a hydrophobic surface with a contact angle of 165 is
shown in Fig. 18. The contact angle between the bubble and particle
increased in the presence of a nanobubble. Fig. 19 schematically
shows a possible mechanism governing the effect of a nanobubble
on an enlarged contact angle (Ahmadi et al., 2014). The increase in
the contact angle increased the attachment force of the particles to
the bubbles, meanwhile decreased the probability of particle
detachment from the bubble (Gontijo et al., 2007). The detachment
probability was also inhibited in the countercurrent column zone
with mixed packing because of a low kinetic energy Ek0 . Recovery
was guaranteed in the cyclone scavenging zone. Qualified
concentrate was obtained with a high height of the froth and wash
water in the FCSMC. In conclusion, the intensification mechanism
of micro-fine low-rank-coal flotation by nanobubbles can be
attributed to the high probabilities of collision and attachment and
low detachment probability.
5. Conclusions
(1) A satisfactory separation performance can be obtained by
using a FCSMC with collector emulsification. The optimal
flotation performance of the FCSMC with emulsified die-
seld17.33% ash content, 90.85% combustible recovery, and
40.79% faultless indexdwas obtained when 6 kg/t of diesel
and 0.18 kg/t of the frother were used.
(2) The improved micro-fine low-rank-coal flotation perfor-
mance by FCSMC can be attributed to as follows: high colli-
sion probability because of turbulent mineralization
mechanism and micro-bubbles; high attachment probability
and low detachment probability because of the introduction
of the hydrophobic attractive force due to the existence of
the nanobubble.
(3) The results in this work demonstrated the potential indus-
trial application of the FCSMC combined with collector
emulsification for micro-fine low-rank-coal flotation. The
outcome of this research provided a new insight into the
flotation of micro-fine low-rank-coal and other difficult-to-
float coal. However, it should be noted that the separation
performance of the FCSMC with highly turbulent minerali-
zation may be limited by high detachment probability for
coarse low-rank-coal in industrial flotation. The ultimate
flotation was the result of the competition between attach-
ment and detachment process. So, satisfactory recovery of
wide-size range particles could not be obtained with the
FCSMC. The flotation recovery of wide-size range low-rank-
coal requires to be studied further.
Please cite this article in press as: Xing, Y., et al., Clean low-rank-coal purification technique combining cyclonic-static microbubble flotation
column with collector emulsification, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.11.057
15
Acknowledgements
This research was supported by the National Nature Science
Foundation of China (51574236), the Project funded by China
Postdoctoral Science Foundation (2014M550317), the Fundamental
Research Funds for the Central Universities(2015XKMS095), the
National Key Technology R&D Program for the 12th Five-Year Plan
of China with Project (Grant no. 2014BAB01B03) and Guizhou “125
plan”key project of science and technology project (No.Qian jiao he
zhong da zhuang xiang zi [2013] 026) for which the authors express
their appreciation.
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