Fuel 207 (2017) 214225

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Fuel
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Full Length Article

Wetting thermodynamics of low rank coal and attachment in flotation

Songjiang Chen b, Zhao Yang b, Liang Chen b, Xiuxiang Tao a,b,, Longfei Tang b, Huan He b
a
Key Laboratory of Coal Processing and Efficient Utilization of Ministry of Education, China University of Mining and Technology, Xuzhou 221116, PR China
b
School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou 221116, PR China

h i g h l i g h t s

The wetting ability of modified diesel oil for coal sample did not entirely increase with the decrease of surface tension, and liquid viscosity was also a
relevant factor.

Great viscosity is good for adhesion, but excessive viscosity was bad for its wettability.

The induction time between coal particles and reactive oily bubbles modified by 2-ethylhexanol and DDAB showed a significant decrease.

It was crucial to the flotation of low rank coal that proper surfactant was used to generate reactive oily bubbles.

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

Article history: It is critical for flotation to accomplish the bubble-mineral particle attachment as well as mineralization
Received 24 March 2017 process. The surface free energy of mineral particle and liquid is a key parameter which affects the wet-
Received in revised form 31 May 2017 tability and wetting process of mineral in mineralization. In this paper, the surface free energy compo-
Accepted 2 June 2017
nents of coal sample were calculated by Washburn equation and Oss Chaudhury-Good-Van theory.
Additionally, the wetting ability of modified diesel oil for coal sample was studied by Washburn dynamic
capillary method while Lipophilic Hydrophilic Ratio and relative contact angle were calculated.
Keywords:
Furthermore, the effect of both surfactants, 2-ethylhexanol and didodecyldimethylammonium bromide
Low rank coal
Wettability
(DDAB), on the induction time between oily bubbles and coal particles was investigated. Results indicated
Surfactant that wetting ability of modified diesel oil for coal sample did not entirely increase with the decrease of
Induction time surface tension, and liquid viscosity was also a relevant factor. The adhesion strength enhanced whereas
Reactive oily bubble flotation the detachment probability reduced with the increase of collector viscosity. But too large viscosity was
bad for fluidity of liquid, which therefore decreased its wettability for coal sample. The induction time
between coal particles and reactive oily bubbles modified by 2-ethylhexanol and DDAB decreased by
74.35% and 86.45% respectively. As a result, the maximum combustible matter recovery of 72.20%
(increasing by 22.23%) and highest flotation efficiency index of 56.50% were obtained when the weight
ratio of 2-ethylhexanol to diesel oil was 0.04, while that of using reactive oily bubbles modified by
DDAB showed an apparent decrease. It indicated that it was crucial to the flotation of low rank coal that
proper surfactant was used to generate reactive oily bubbles.
2017 Elsevier Ltd. All rights reserved.

1. Introduction
Coal is taken as the main energy source, and coals share of Chi-
nas primary energy consumption is 64% in 2015. Whats more,
there are abundant resources of low rank coal in China, which
accounts for 45.68% of proven coal reserves [1]. Production of
low rank coal reached to 1.8 billion tons in 2013, accounting for
Corresponding author at: Key Laboratory of Coal Processing & Efficient
Utilization, School of Chemical Engineering and Technology, China University of
Mining and Technology, 221116 Xuzhou, PR China.
E-mail addresses: csj2014@cumt.edu.cn (S. Chen), taoxx163@163.com (X. Tao).
about 50% of total coal production capacity, which had been an
important part of Chinas coal energy production and supply.
However, the economical recovery of low rank coals is difficult
to achieve, which restricts its clean and efficient utilization. For
low rank coal molecule, it has the characterize of less condensed
aromatic ring, high H/C ratio, much aliphatic chains and great
amount of oxygen which exists mainly in the form of polar hydro-
xyl (both phenol and alcohol), carbonyl and some peroxide type
oxygenated moieties [25]. These hydrophilic functional groups
decrease hydrophobicity of low rank coal thus lead to poor floata-
bility [6,7]. The adhesion efficiency of diesel oil droplets onto low
rank coal surface is so small that large amount of collector is

http://dx.doi.org/10.1016/j.fuel.2017.06.018
0016-2361/ 2017 Elsevier Ltd. All rights reserved.
 S. Chen et al. / Fuel 207 (2017) 214225
required to achieve satisfactory yields [7,8]. Furthermore, there are
a lot of oxygen and nitrogen atoms on the surface of low rank coal,
which are easily negatively charged and then bring about the
stable hydration film. Hydroxyl and carbonyl of coal surface can
also be ionized, which can influence the flotation process by con-
trolling the thickness of liquid film on coal surface. Consequently,
it is difficult to float the low rank coal using common oily collec-
tors, such as diesel oil and kerosene [9].
For fine materials under 0.5 mm, flotation is the most efficient
separation technology [10]. Bubble-mineral particle attachment
and mineralization process are critical to flotation which can real-
ize the effective separation of coal and gangue. The surface free
energy (for liquid also called surface tension) of mineral particle
and liquid is a critical parameter which affects the wettability
and wetting process of mineral in mineralization [11]. Therefore,
the attachment and mineralization process between bubbles and
particles can be analyzed from the respect of thermodynamics. If
the free energy of the system is reduced, the adhesion process
can be carried out spontaneously. The strong surface hydrophobic-
ity of ore particles is corresponding to the great contact angle of
the water to the coal sample and the strong spontaneous tendency.
For liquid, the surface free energy is equal to that of the surface
tension in values. While, for solid, according to the Van OssCha
udhuryGood theory, the total surface free energy can be decom-
posed into the non-polar Lifshitz-vander Waals force and polar
Lewis acidbase interaction force [1216]. Van Oss, Good et al.
[17,18] thought that H-bonds were attributed to polar Lewis
acidbase which was composed of acid part and base part. Wash-
burn dynamic method and Oss Chaudhury-Good-Van theory can
be used to measure and calculate the total surface free energy of
solid and its components thus learn the wetting behavior of min-
eral dust. The detailed description can be found in other literatures
[11,12,19]. Additionally, Lipophilic Hydrophilic Ratio [12,20], wet-
ting energy, film flotation and induction time measurement are
also used to determine surface energy [21,22].
In order to enhance surface hydrophobicity of low rank coal,
pretreatments are always necessary. The main pretreatment meth-
ods consist of preconditioning and grinding [23,24], thermal [25]
and microwave [26], ultrasound [27], direct contact mixing of the
reagents with dry coal before wetting [28], which improve the
hydrophobicity of low rank/oxidized coals by reducing the oxy-
genated functional groups on the coal surface thus making some
fresh surfaces, removing pore water and hydration water, avoiding
formation of a thick wetting film on the coal surface or modifying
the surface. Furthermore, it is called reactive oily-bubble flotation
that air bubbles are replaced by reactive oily bubbles (i.e., bubbles
covered by a thin layer of non-polar collector modified by surfac-
tants) as a carrier in flotation [29]. For minerals difficult to float,
the experimental results showed better flotation efficiency using
reactive oily bubbles than that of air bubbles because of formers
stronger collecting power, better selectivity and shorter induction
time. Therefore, reactive oily-bubble flotation has been proven to
be a more effective technology [3036]. There are a number of
advantages in reactive oily-bubble flotation in which a non-polar
collector modified by surfactants is not directly added into the
pulp, but as a thin hydrophobic layer covering on bubble surface
comparing with the conventional flotation. It reduces the actual
amount of collector required by greater degree of dispersion on
target particles and minimizes undesired activation of gangue par-
ticles. Whats more, a higher concentration of collector molecules
localized on the oil-water interface gives rise to a stronger collect-
ing power [29]. When adsorption between the collector film and
the mineral particles happens, the mineral particles also adheres
to the bubbles, thus reducing the adhesion work and greatly
decreasing the induction time.
215
The thinning and rupture of wetting thin films between the air/
water and solid/water interfaces, and the formation and expansion
of the gasliquidsolid contact lines must be done after collision
for bubble-particle attachment to occur. The attachment time is
defined as the time for the attachment process involving three
events, while the induction time is a part of attachment time and
is referred to the time for the first two processes [37]. For attach-
ment and mineralization to occur, the induction time must be less
than the contact time. Therefore, the induction time is a quite
important parameter for the separation of coal and mineral matter.
Albijanic et als [37] work reviewed the experimental studies into
the induction and attachment times between minerals and air bub-
bles as well as oil droplets and air bubbles. The results showed that
the changes of surface of pure minerals in both flotation surface
chemistry and physical properties could be determined by the time
parameters. Su et als [36] research, which focuses on the mecha-
nisms of oily bubbles improving bitumen recovery, indicated that
the spreading of oily bubbles on a bitumen surface was much faster
than that of air bubbles, the induction time between oily bubbles
and bitumen was much shorter than that of air bubbles and bitu-
men, which was well correlated with higher recovery using oily
bubbles as a carrier in flotation.
In the present work, the reactive oily-bubble flotation was
employed to enhance the flotation of low rank coal. While, 2-
ethylhexanol and didodecyldimethylammonium bromide were
used as emulsifiers to improve the performance of oily bubbles.
The wetting ability of modified diesel oil for coal sample was stud-
ied by Washburn dynamic capillary method while it was evaluated
by Lipophilic Hydrophilic Ratio. Moreover, the attachment effi-
ciency between reactive oily bubbles and coal particles was esti-
mated by induction time.
2. Washburn equation and Van OssChaudhuryGood theory
According to Poiseuille law [38] and Laplace equation, the
Washburn equation can be expressed as follows [39]:
q2 cL cosh
x2 c t 1
2g
where x is the liquid weight gain. c is the geometric factor of Wash-
burn tube (The geometric factor c of the packed Washburn tube is
the same for one kind of sample and the same Washburn tube). q
is the density of the liquid. cL is the surface tension of liquid. g is
the liquid viscosity. h is the contact angle. And t is the wetting time.
The geometric factor of packed Washburn tube is
c rC 2 pR2 2
where r is the effective radius of capillary. C is fine particle filling
rate in Washburn tube. R is the radius of Washburn tube.
The slope of w2-t, k is
q2 cL cosh
k 3
2g
The geometric factor of packed Washburn tube can be deter-
mined by choosing one kind of probe liquid as a reference liquid
with the fastest wetting rate for particle sample. The difference
of wettability of liquids for particle samples can be evaluated by
wetting rate and relative contact angle.
Lipophilic Hydrophilic Ratio (LHR) is used to evaluate the differ-
ence of wettability of oil (L) and water (H) for the solid sample and
is given by:
coshL kL gL q2H cH
LHR  4
coshH kH gH q2L cL
216 S. Chen et al. / Fuel 207 (2017) 214225

When the interfacial tension in the three-phase system of solid, content, Vad the volatile matter content, FCad the fixed carbon
liquid and gas reaches equilibrium, Young equation [11] can be content, and Cdaf, Hdaf, Odaf, Ndaf, and Sdaf are the content of carbon,
expressed as follows: hydrogen, oxygen, nitrogen and sulfur, respectively. The size frac-
tion of 0.0740.125 mm was collected by wet screening from
cS cSL cL cosh 5
below 0.5 mm of slime. Then the coal sample was stored in a dry
That is dish after drying at 60 C for 5 h for induction time measurement.
cS  cSL Diesel oil was used as the flotation collector, and 2-
cos 6 ethylhexanol and didodecyldimethylammonium bromide (DDAB)
cL
were used as surfactants to enhance the collecting power
According to Van OssChaudhuryGood theory, the surface free and selectivity of collector. Formamide, n-hexane, a-
energy of the solid and liquid are given by [4042]: bromonaphthalene and deionized water were used as probe
q liquids.
cS cLW
S cS cS 2
AB LW
cS cS 7

q 3.2. Methods
cL cLW
L cL cL 2
AB LW
cL cL 8
3.2.1. SEM measurement
where cS and cL are respectively the total surface free energy of Quanta 250 Scanning Electron Microscope (SEM) for the analy-
solid and liquid, cSLW and cLW
L are respectively the non-polar part sis of surface morphology of coal particles was at Advanced Anal-
of solid and liquid, cSLW and cLW
L are the polar parts, c+S and c+L are ysis & Computation Center of China University of Mining &
the acid parts, and cS and cL are the base parts.
 
Technology. The conductive tape was adhered to the sample holder
The interfacial free energy between solid and liquid is plainly, on which evenly coated a layer of coal particles. Particles
expressed: failed to strongly adhering on the conductive tape were blown
q q2 off by bulb syringe and then the surface was plated with gold pow-
cSL cLW
S  cLW
L
der for conductive in scanning test.
q q q q
2 cS cS cL cL  cS cL  cS cL 9 3.2.2. FT-IR measurement
The functional groups of coal material were determined by
That is Fourier Transform Infrared Spectroscopy (Vertex 80v, Bruker) with
q scanning range of 4000400 cm1, wave number accuracy of less
cSL cLW
S cL  2
LW
cLW
S cL
LW than 0.1 cm1, scanning frequency of 32 and spectra resolution
q q q q power of 4 cm1. Coal samples with grain size of less than
2 cS cS cL cL  cS cL  cS cL 10 0.074 mm prepared by grinder homogeneously mixing with potas-
sium bromide (KBr) were pressed into a pellet through 20 MPa
Combining Eqs. (7) and (8), so the Eq. (10) changes to pressure.
q q q
cSL cS cL  2 cLW
S cL  2
LW
cS cL  2 cS cL 11 3.2.3. Surface tension and wetting process measurements
Surface tension and wetting ability measurements of modified
Eq. (12) is combined Eqs. (5) and (11)
 diesel oil were performed with Tensiometer K100 (KRUSS) at key
q q q q
Laboratory of Coal Processing and Efficient Utilization in China.
cLW
L 2 cL cL 1 cosh 2 cLW
S cL
LW
cS cL cS cL
Dunouy ring method and sorption methods were employed in
12 these measurements respectively. No less than 30 mL probe liquid
or collector liquid was filled in the glass beaker in the measure-
Surface free energy and its components of the coal sample can ments. About 2.000 g coal sample below 0.074 mm in diameter
be calculated by measuring advancing contact angle wetted by prepared by grinder was weighed and filled into a clean Washburn
three kinds of liquids by Eq. (12) which surface free energy and tube. There is a circular filter paper placed on the bottom of Wash-
its components are known. burn tube to avoid the particles in the tube falling down. Try to
ensure that there is a strict uniform degree of compaction every
3. Materials and methods test so as to make it with the same capillary constant and repro-
ducible results. In addition, n-hexane was used as the reference liq-
3.1. Materials uid to determine the capillary constant of Washburn tube for one
coal sample. Then Washburn tube was fixed vertically on the
The coal slime less than 0.5 mm from Daliuta coal preparation microbalance of the Tensiometer K100. Lift the glass beaker slowly
plant in Shanxi Province of China was used as the experimental by elevator-platform until the distance between liquid level and
material of oily-bubble flotation, which is a kind of Non-caking Washburn tube bottom is about 2 mm. 600 s and 200 data points
coal. The proximate and ultimate analyses of coal sample are were set to detect the mass change of the Washburn tube. In each
shown in Table 1, where Mad is the moisture content, Aad the ash measurement, three trails were conducted for the reproducible

Table 1
Proximate and ultimate analyses of coal sample.

Proximate analysis, % Ultimate analysis, %

Mad Aad Vdaf FCdaf Cdaf Hdaf Odaf Ndaf Sdaf
7.68 33.98 36.68 63.32 68.38 3.90 24.55 1.14 2.03
 S. Chen et al. / Fuel 207 (2017) 214225
result. The detailed description of the method can be found else-
where [11,12,19].
3.2.4. Induction time measurement
The induction time measurement between oily bubbles and
coal particles was conducted with 2015EZ Induction Timer Instru-
ment as shown in Fig. 1, which is mainly composed of a power dri-
ver (a 40-watt speaker with a frequency range of 9015,000 Hz), an
integrated control box, a CCD camera system with a macro lens, a
Z4D-F04A micro-displacement sensor, an illumination device, a
sample table with heating device, a device generating bubbles
and a work station.
0.0740.125 mm of Daliuta coal particles were used in this
measurement. Before the test, a flat and even thickness of coal par-
ticle bed was required. Fig. 2 shows the induction time measure-
ment. A controllable size air bubble was generated at the end of
the capillary tube using a micro syringe. Then the distance
between the bubble and the particle bed was adjusted using the
three-dimensional micro-translation stage with the aid of a macro
lens connected to a CCD camera. And the movement of an air bub-
ble was controlled by the speakers drum via a capillary tube drove
by an amplifier interfaced with a computer. Additionally, a micro-
displacement sensor was used to detect the actual displacement of
the speakers drum. Furthermore, there are 0.1 ms resolution of the
duration and 0.2um resolution for the amplitude of the displace-
ment respectively. The measurement was conducted by moving
the bubble towards and then touching the mineral particle bed
for a given period of time before retracting away from the mineral
particle bed. With the aid of the macro lens linked to the CCD cam-
era, attachment process and result can be observed. Obviously,
there will be bubble-particle attachment to be observed if the con-
tact time is long enough, otherwise, there will be no particle to be
picked up by the bubble. The detailed description of this measure-
ment can be found elsewhere [43,44]. In the measurement, the
minimum time that bubbles can pick up the particles every contact
was defined as the induction time.
3.2.5. Oily bubble flotation tests
Flotation tests were conducted with an oily bubble flotation
system, as shown in Fig. 3a, to confirm the feasibility of reactive
oily bubble flotation for low rank coal. The detailed parameters
of flotation and specific procedures can be seen in Table 2 and
Fig. 3b respectively. Firstly, the suspension of 90 g of coal sample
and 1.5L of water was conditioned at 2000 rpm for 120 s. Then,
0.045 mL (0.4 kg/t) foaming agent (MIBC) was added to the pulp
with micro syringe and another agitating for 120 s was needed.
Meanwhile, the collector (6.875 kg/t), diesel oil or the mixture of
diesel oil and 2-ethylhexanol/DDAB, was held in an atomizer and
then dispersed into fine oil drops by air compressed atomizer.
Fig. 1. Image of induction timer instrument.
217
Open the inlet valve, the diesel oil drops and air were inhaled into
flotation cell. The air in the flotation cell was sheared by the
high-speed rotating impeller into a large volume of air bubbles
containing diesel oil drops. These diesel oil drops moved to the sur-
face of the bubbles in a very short time and spread on its surface
(i.e., bubble surface was covered by a thin layer of collector),
namely oily bubble. Finally, start the scraper to collect the froth
concentrates for 300 s. The froth concentrates and flotation tailings
were vacuum dried, weighed and taken for ash analysis to achieve
the last recovery of combustible matter.
4. Results and discussions
4.1. SEM analysis
As is shown in Fig. 4, SEM measurements demonstrate that the
coal surface is characterised by roughness, irregular strips, plenty
of cracks with width under 1 lm, and fine particles (<5 lm) are
mixed in these cracks. In flotation, cracks in coal surface could
be easily filled by water, deteriorating the hydrophobicity of coal
particals, thus increasing the resistance of attachment between
particles and bubbles. Whats more, organic material and inor-
ganic material can be easily distinguished by the technology of
Backscattered Electron Imaging. Metallic minerals like pyrite
possess the highest luminance in Backscattered Electron Image
while organic material is inversely different. Meanwhile, clay
minerals, quartz, calcite and dolomite own the modest luminance.
In Fig. 4b, except for the embedded calcium carbonate as seen in
Fig. 5 in the splendent region labeled A, other parts are organic
materials.
4.2. FT-IR analysis
Chemical properties of coal surface could be obtained by analy-
sis of Fourier Translation Infrared Spectrum. After a calibration of
baseline and normalization, the spectrum is shown in Fig. 6a.
Peak-differentation-imitating analysis for original FT-IR spectra
was conducted and the results are illustrated in Fig. 6b and c.
Detailed analysis parameters for chemical groups has been shown
in Table 3. In Fig. 6c, there is a strong C@C-stretching vibration
absorption peak at 1596.34 cm1 and the relative absorbance is
0.9277. In Fig. 6b and c, it can be determined that the absorption
peaks NO. 3 and 5 are caused by aromatic hydrocarbon; NO. 4
and 10 absorption peaks represent carboxylic acid; The coupling
effect of C-OH stretching vibration and COH bending vibration
caused absorption peaks numbered 7 and 9. Combined the relative
absorbance and peak area, it can be concluded that the oxygen in
Daliuta coal sample is mainly exist as alcoholic hydroxyl group
and phenolic hydroxyl group, the second most is carboxyl and only
218 S. Chen et al. / Fuel 207 (2017) 214225

Fig. 2. Attachment process between coal particles and bubbles.

Fig. 3. Oily bubble flotation system (a) and test procedure (b).

Table 2
Parameters of oily bubble flotation.

Pulp concentration Impeller speed Air flow rate Dosage of collector Dosage of foaming agent
60 g/L 2000 r/min 0.25 m3/h 0.15 mL/min 45 lL

Fig. 4. SEM photographs of coal sample, (a): 1200X; (b): 5000X.

a little of them are formyl group and ether. These oxygen func- 4.3. Surface free energy of coal particles
tional groups can form hydrogen bonds with water molecules
thereby enhance hydrophilicity of coal particles, making low rank A K100 Surface Tension Meter was used to measure the
coal difficult to float. samples surface tension. In this measurement, four reagents
 S. Chen et al. / Fuel 207 (2017) 214225 219

cps/eV

8
7
6
5
CaO
4 C Al Ca

3
2
1
0
2 4 6 8 10 12 14 16 18 20
keV
Fig. 5. Energy spectrum diagram of point A.

Fig. 6. FT-IR spectra of 0.0740.125 mm coal sample, (a): Original FT-IR spectra; (b): Peak-differentation-imitating analysis of 40002600 cm1 in FT-IR spectra; (c): Peak-
differentation-imitating analysis of 1800400 cm1 in FT-IR spectra.

respectively are n-hexane, a-bromonaphthalene, formamide, Fig. 7 is a diagram of the coal samples wetting process by four
deionized water were applied to obtain relevant parameters, as reagents mentioned above. In order to reduce error, the initial sev-
shown in Table 4. To clarify specially, the n-hexane was used to eral points and wetting equilibrium point were removed. After a
determine the Washburn tube constant [15,45]. linear regression with least square method, LHR value was figure
220 S. Chen et al. / Fuel 207 (2017) 214225

Table 3
Detailed analysis results for chemical groups.

Peak Wavenumber, cm1 Relative absorbance Relative peak area, % Chemical group
1 3384.31 0.2486 1.3405 Phenol(ArAOH) OAH stretching vibration
2 3186.02 0.1675 4.8943 Alcohol(RAOH) OAH stretching vibration
3 3057.93 0.0744 9.4341 Aromatic ring CAH stretching vibration
4 1692.39 0.2434 2.4936 Dimer carboxylic acids C@O stretching band
5 1596.34 0.9277 14.0582 Aromatic ring C@C stretching vibration
6 1437.90 0.3563 3.2434 Carboxylic acids COH in-plane bending vibration
7 1256.94 0.6417 10.7279 Alcohol CAOH stretching vibration and COH in-plane bending vibration
8 1169.08 0.7980 11.4733 Phenol CAOH stretching vibration
9 1096.29 0.6946 8.3133 Alcohol CAOH stretching vibration and COH in-plane bending vibration
10 939.26 0.2128 3.3436 Dimer carboxylic acids COH out-of-plane bending vibration
11 769.25 0.2415 3.2511 Alcohol or phenol COH out-of-plane bending vibration

Table 4
Surface free energy parameters of probe liquids (at 20 C) .

Probe liquids Density Viscosity Surface tension c L LW c L+ c L

g/cm3 mPas mN/m
n-Hexane 0.661 0.326 18.40 18.40 0 0
a-Bromonaphthalene 1.483 5.107 44.40 44.40 0 0
Deionized water 0.998 1.002 72.80 21.80 25.50 25.50
Formamide 1.133 3.812 58.00 39.00 2.28 39.60

surface. The results are corresponding to the SEM measurements

and FT-IR spectra measurements. In flotation, the cationic surfac-
tant is more likely to adsorbed in the alkaline surface by the func-
tion of electrostatic attraction.

4.4. Wetting thermodynamics analysis

Two type of surfactants, 2-ethylhexanol and DDAB, were used

in the experiment to enhance the surface activity and selectivity
of collector. The mixing ratio and serial number is shown in
Table 7.

4.4.1. Surface tension and viscosity of reagent

Fig. 7. Wetting process of coal sample by probe liquids.
out using Eq. (4). Washburn tube constant was used to calculate
relative contact angle, as shown in Table 4. It is obvious that the
wetting rate is in the order as follows: n-hexane > a-
bromonaphthalene > formamide > deionized water.
Inserting the data of Tables 3 and 5 into Eq. (12) gives a series of
surface free energy parameters, as shown in Table 6. It can be con-
cluded that the sample used is low in surface energy. Polar compo-
nent in the coal surface takes only 11.413%. On the other hand,
alkaline component plays a major role in polar part, maybe is
caused by the major oxygen-containing functional groups in coal
Surface tension and viscosity is the evaluation indicator of mod-
ification effect of surfactant. The result is given in Figs. 8 and 9. As
is seen in Fig. 8, the surface tension of Num. C2 diesel decreased
dramatically as the increasing weight ratio of 2-ethylhexanol,
meanwhile, the viscosity is lowest when the weight ratio is 0.02
and it increased with the increase of weight ratio. On the other
hand, DDAB has a great effect both on the surface tension and vis-
cosity. Fig. 9 shows that the surface tension decreased sharply
while the viscosity increased a lot. The maximum increasing scale
of viscosity is 197.56% at the weight ratio of 0.15. Compared to
conventional surfactants, dimeric surfactants consist of two
amphiphilic groups, making the molecule has greater interfacial
activity. In flotation, lower surface tension will contribute to the
dispersion of collector on coal surface. And higher viscosity is
expected to enhance the adhesion between modified diesel oily
bubbles and coal particles.

Table 5
Values of wetting process of coal sample by n-hexane, a-bromonaphthalene, deionized water, formamide.

Probe liquids DaLiuta coal sample

Wetting rate Adj.R-Square LHR relative contact angle (h)/() cosh
(104g2/s)
n-Hexane 40.05 0.996 12.91 0 1.000
a-Bromonaphthalene 16.03 0.991 6.67 58.91 0.516
Deionized water 9.14 0.999 85.56 0.077
Formamide 3.51 0.944 1.43 83.66 0.110
 S. Chen et al. / Fuel 207 (2017) 214225 221

Table 6
Surface free energy parameters of coal sample.

Surface free energy (mJ/m2) Polar component (%)

cS cS LW
cS +
c 
S c S
AB

28.798 25.511 0.464 5.820 3.287 11.413

Table 7
Mixing ratio and serial number of modified diesel.

Serial 2-ethylhexanol-diesel oil Serial DDAB-diesel oil

number weight ratio number weight ratio
C 0 C 0
C21 0.02 CS1 0.02
C22 0.04 CS2 0.04
C23 0.06 CS3 0.06
C24 0.10 CS4 0.10
C25 0.15 CS5 0.15

Fig. 10. Wetting curves of coal sample by C2.

Fig. 8. Curves of reagent C2 surface tension and viscosity.

Fig. 11. Wetting curves of coal sample by CS.

2-ethylhexanol can improve the wettability of diesel on coal parti-

Fig. 9. Curves of reagent CS surface tension and viscosity.
4.4.2. Wetting thermodynamic behavior of coal sample
Wettability, an important property of collector, is used to eval-
uate the modification effect of surfactants. The wetting curve is
shown in Figs. 10 and 11. The same computing method as
described above was used to calculate LHR values and relative
contact angle, as shown in Tables 8 and 9. It is indicated that
cles whereas DDAB has a negative effect. The wetting rate
increased dramatically after the dosages of 2-ethylhexanol exceed
2% and reached maximum value when the weight ratio is 0.04, and
then it leveled off. In contrast, a small quantity of DDAB caused
sharply decrease of wetting rate and it leveled off after the weight
ratio reached 0.06. Combined with the analysis of surface tension
and viscosity, it is found that the wettability of modified diesel is
not absolutely in inverse proportion to surface tension. Viscosity
and structure of surfactant are relevant crucial parameters.
Increased viscosity decreased floatability of liquid and thus wet-
ting rate was decreased. With little change of viscosity, the wetting
rate of modified diesel could increase with the decreasing of sur-
face tension until a critical concentration of surfactant. When crit-
ical value is reached, viscosity will become a predominant factor
over surface tension at the weight ratio of 0.06 as seen in Fig. 8
and Table 8.
222 S. Chen et al. / Fuel 207 (2017) 214225

Table 8
Calculated results of LHR and relative contact angle for C2.

Probe liquids Daliuta coal sample

Wetting rate Adj.R-Square LHR relative contact angle (/()
(104g2/s)
n-Hexane 40.05 0.996 12.910 0
C 7.76 0.991 9.676 41.49
C21 7.96 0.995 9.692 41.38
C22 9.38 0.992 11.534 26.76
C23 8.00 0.995 9.862 40.23
C24 8.41 0.995 10.631 34.61
C25 8.34 0.996 10.783 33.41

Table 9
Calculated results of LHR and relative contact angle for CS.

Probe liquids Daliuta coal sample

Wetting rate (104 g2/s) Adj.R-Square LHR Relative contact angle (/()
n-Hexane 40.05 0.996 12.910 0
C 7.76 0.991 9.676 41.49
CS1 3.85 0.997 5.169 66.40
CS2 2.80 0.957 4.314 70.48
CS3 1.84 0.955 3.327 75.07
CS4 1.31 0.972 3.079 76.20
CS5 0.78 0.964 3.013 76.50

4.5. Induction time
Attachment time is used to predict adhesion efficiency of parti-
cles and bubbles, which is an expression of modification effect of
surfactant. The result is shown in Fig. 12. Using 2-ethylhexanol,
the attachment time decreased by 74.35% in the largest scale and
it decreased slowly after the weight ratio exceeds 0.02. In addition,
DDAB reduced the attachment time more effectively, by 86.45%.
The variation tendency along with weight ratio is similar to that
of 2-ethylhexanol. There are reasons to believe surfactants could
promote the dispersion and spreading of diesel molecules by
reducing surface tension, thus reducing adhesion energy. Besides,
it should be noticed that date points of CS1, CS2 and CS3 show a
shorter induction time than that of C23, C24 and C25 respectively
although with similar values in surface tension as seen in Figs. 8
and 9. Viscosity maybe is another important parameter for
Fig. 12. Induction time between coal particle and reactive oily bubble modified by
2-ethylhexanol and DDAB.
attachment by a way of increasing adhesion force and reducing
striping rate.
4.6. Flotation results
The recovery of combustible matter and flotation efficiency
index using reactive oily bubble modified by nonionic surfactant
2-ethylhexanol and ionic surfactant DDAB as functions of weight
ratio are shown in Fig. 13a and b. The concentrate with ash content
of 10.07%, maximum combustible matter recovery of 72.20%
(increasing by 22.23%) and high flotation efficiency index of
56.50% were obtained for coal sample when the weight ratio of
2-ethylhexanol to diesel oil was 0.04, as shown in Fig. 13a. Only
based on the results of induction time measurement not on the
outcomes of wettability measurement for coal sample particles, a
better flotation performance is expected for the flotation using
reactive oily bubble modified by DDAB. However, it is observed
that combustible matter recovery and flotation efficiency index
decreased dramatically while ash content of concentrate increased
with the increase of the weight ratio of DDAB to diesel in Fig. 13b,
which was well consistent with the results of wetting ability stud-
ies of the agents for coal sample particles. It showed obviously
lower combustible matter recovery and higher ash content of con-
centrate (over 33.98% at weight ratio of 0.10 and 0.15) compared
with that of diesel oily bubbles as well as reactive oily bubbles
modified by 2-ethylhexanol, i.e., it indicated bad selectivity for coal
and unexpected stronger collecting power for gangue at high con-
centration of DDAB. Hence, there are reasons to believe that the
energy required by the oily collector spreading on the coal surface
is reduced because of 2-ethylhexanols adsorption at the coal/
water interface and coal/oil interface. In addition, reactive oily
bubbles modified by 2-ethylhexanol showed a stronger collecting
power and selectivity than that of modified by DDAB. Furthermore,
hydroxyl functional groups in 2-ethylhexanol played a crucial role
by directional adsorption on polar oxygen-containing functional
groups of coal surface by hydrogen bonding, which enhanced the
hydrophobicity of coal [11]. However, DDAB with a negative effect
may be attributed to that DDAB as an ionic surfactant has the
 S. Chen et al. / Fuel 207 (2017) 214225
Fig. 13. Curves of coal sample flotation with reactive oily bubbles modified by 2-ethylhexanol (a) and DDAB (b).
characteristic of being more readily soluble in water thus adsorb-
ing on coal surface when present in sufficient quantities, making
the coal hydrophilic. And it is more easily adsorbed on gangue par-
ticles negatively charged by the function of electrostatic attraction,
which thus enhances the unexpected collecting power for gangue.
On the other hand, excessive viscosity leading to merger of reactive
oily bubbles modified by DDAB decreases its performance.
In order to better understand this phenomenon, the SEM and
FT-IR analyses for flotation concentrates and tailings were per-
formed and the results are shown in Figs. 14 and 15, respectively.
Compared with raw coal, a large amount of ultra-fine particles
adsorbed on the surface of coarse particles as seen in Fig. 14a,
which exactly suggested that adsorption of the collector/mixed
collector on the surface and in pores happened. This adsorption
of the collector/mixed collector increased the hydrophobic site
thereby made coal particles easier to attach themselves to bubbles.
However, it should be noted that there was almost no adsorption of
collector on the gangue minerals in the concentrates and/or tail-
ings of reactive oily bubble flotation using C24 as seen in
Fig. 14a and b, so the minerals could not float and was left in the
flotation pulp. As a result, a good flotation performance was
obtained by using 2-ethylhexanol. In contrast, the adsorption of
collector on the surface of both coal and gangue minerals, espe-
cially more adsorption on gangue minerals, was observed, when
223
CS5 was used to generate oily bubbles as shown in
Fig. 14c and d, which made the gangue minerals more easily to
transfer into the froth products. Therefore, it led to a bad flotation
performance, i.e., a bad collecting power and selectivity.
Fig. 15 showed the results of FT-IR analysis for the raw coal and
flotation concentrates and tailings. The relative absorbance of
peaks at 3398, 2919, 2850, 1597, 1433, 1375 and 1163 cm1 corre-
sponding to organic matters in coal showed a significant increase
in the flotation concentrates using C24, while the density of peaks
at 425, 913, 1032 and 1009 cm1 corresponding to the chemical
groups of FeAS (FeS2), SiAOAAl, SiAOASi and SiAO respectively,
i.e., gangue minerals, showed an obvious decrease. Meanwhile, it
was observed that the relative absorbance of peaks of 32303440
and 1433 cm1 representing hydroxyl group (phenol/alcohol
OAH stretching vibration) increased more significantly. However,
there was almost no combustible matter in the tailings as seen in
Fig. 15. It verified the directional adsorption of hydroxyl functional
groups in 2-ethylhexanol on polar oxygen-containing functional
groups of coal surface and indicated a better collecting power
and selectivity, which was well agreed with the SEM analysis
and flotation results. On the contrary, most of organic matters were
concentrated in the tailings rather than in the clean coal of flota-
tion using CS5, showing a bad collecting power and selectivity,
which also well agreed with the SEM analysis and flotation results.
224 S. Chen et al. / Fuel 207 (2017) 214225
Fig. 14. SEM photographs of flotation concentrates and tailings: (a) the concentrates and (b) the tailings of reactive oily bubble flotation using C22, (c) the coals and (d) the
minerals in the froth products of reactive oily bubble flotation using CS5.
Fig. 15. FT-IR spectra of raw coal sample and flotation products.
5. Conclusions
The wetting ability of diesel oil modified by 2-ethylhexanol and
DDAB for low rank coal sample was investigated with Tensiometer
K100 through Washburn dynamic capillary method, and the effect
of both surfactants on the attachment between reactive oily bub-
bles and coal particles was evaluated by induction time and oily
bubble flotation tests. The surface free energy components of coal
sample were calculated to be 28.798 mJ/m2, which indicated that
the coal was a material in low surface energy. 2-ethylhexanol
and DDAB both decreased the surface tension of modified diesel
oil, which promoted its dispersion on coal surfaces and improved
the wetting ability of modified diesel oil for coal sample, enhancing
the attachment of coal particles to oily bubbles. Meanwhile, both
surfactants had an effect on viscosity of modified diesel oil, and
the increasing viscosity enhanced the adhesion strength and
reduced the detachment probability. However, it should be noted
that excessive viscosity was bad for fluidity of collectors as well
as their wettability for coal sample. It suggested that the attach-
ment process and the wetting ability of modified diesel oil for coal
sample did not only depend on the surface tension but also on the
liquid viscosity. As a result, the induction time between coal parti-
cles and reactive oily bubbles modified by 2-ethylhexanol and
DDAB showed a significant decrease, from 51.67 ms down to
13.25 and 7.00 ms respectively, when the weight ratio was 0.15.
Correspondingly, the maximum combustible matter recovery of
72.20% and highest flotation efficiency index of 56.50% were
obtained when the weight ratio of 2-ethylhexanol to diesel oil
was 0.04. On the contrary, the flotation using reactive oily bubbles
modified by DDAB showed an unexpected bad performance. Con-
sequently, it was concluded that it was critical to the flotation of
low rank coal to use appropriate surfactant to generate reactive
oily bubbles.
 S. Chen et al. / Fuel 207 (2017) 214225
Acknowledgement
This study was supported by the National Natural Science Foun-
dation of China (Grant No. 51574235).
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