Applied Clay Science 143 (2017) 437–444

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Applied Clay Science

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Research paper

Removal of fine quartz from coal-series kaolin by flotation MARK

a,b b,⁎ a,⁎⁎ a c a
Xiangning Bu , Geoffrey Evans , Guangyuan Xie , Yaoli Peng , Zungan Zhang , Chao Ni ,
Linhan Geb
a
School of Chemical Engineering and Technology, China University of Mining and Technology, 1 Daxue Road, Xuzhou 221116, Jiangsu, PR China
b
Discipline of Chemical Engineering, School of Engineering, University of Newcastle, 2308, Australia
c
Xuzhou Products Quality Supervision & Inspection Center, Xuzhou 221000, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Coal-series kaolin (CSK) in Xuzhou, Jiangsu Province of Eastern China was characterized by chemical analyses,
Coal-series kaolin X-ray diffraction (XRD) and zeta potential measurement as well as by scanning electron microscope equipped
Flotation with an energy dispersive spectrometer (SEM-EDS). The authigenic ultrafine quartz grains (d90 = 15.8 μm)
Dodecyl amine closely associated with this CSK sample was the major impurity mineral, which cannot be separated from kaolin
Quartz
by screening and size classification process. This work investigated the separation of fine quartz from kaolin by
Depressant
flotation. Single mineral flotation tests indicated that effective separation of quartz from kaolin was possible
with acidic pH value (pH = 3), depressant of starch and collector of dodecyl amine (DDA). Rougher flotation
tests of coal-series kaolin revealed that the SiO2/Al2O3 weight ratio of the concentrate was qualified for
industrial applications in the presence of 160 g/t starch and 100 g/t DDA, at acidic pH pulp. A specially designed
two-stage cleaner flotation flowsheet increased the concentrate recovery from 37.26% to 46.55% compared to a
rougher flotation process.

1. Introduction
Kaolin, also known as china clay, is a relatively pure clay pre-
dominantly consisting of kaolinite (Al2O3·2SiO2·2H2O) having a SiO2/
Al2O3 weight ratio of 1.18, which is important in geology, agriculture,
construction, engineering, process industries, and environmental appli-
cations (Jones et al., 1992; Murray, 2000). Kaolin finds application in a
variety of industries like paper, ceramics, rubber, plastics, cement, ink,
catalyst, fiber glass (Mohammadi and Pak, 2003; Murray, 1963). Kaolin
can also be used in the environment as a natural scavenger of pollutants
by removing pollutants either through ion exchange or adsorption,
which makes it a very promising low cost adsorbent for water treatment
(Rafatullah et al., 2010).
Kaolin extracted from commercial deposits contains kaolinite as a
major component along with organic material and other minerals, such
as quartz, muscovite, limonite, anatase, hematite, and illite (Saikia
et al., 2003). These ancillary minerals are deleterious since they
adversely affect the properties and make kaolin unsuitable for many
applications. Hence, their removal is of prime importance in order to
achieve the optimum utilization of kaolin. The methods of beneficiation
depend upon the quantity and nature of the impurity minerals
associated with the clay. Common techniques involve: (I) size classifi-
cation for removing coarse minerals and for attaining the specific
particle size distribution, (II) magnetic separation of the colored
minerals containing iron for improving the brightness, (III) chemical
bleaching for removing organic coloring impurities (oxidative) and iron
minerals (reductive), and sometimes, (IV) froth flotation to separate
micaceous, graphitic and titanoferrous minerals (Jepson, 1988; Liu
et al., 2017; Newns and Pascoe, 2002; Raghavan et al., 2004).
Coal-series kaolin (CSK) deposits, found in coal seams of coal mines,
are mainly concentrated in northwest China with large reserves found
in Shanxi, Sanxi, Inner Mongolia, Xinjiang, Jiangsu and Henan
Provinces (Wilson, 2004). Kaolin minerals (SiO2/Al2O3 weight ratio <
1.29) are used for coating in the paper industry; and the presence of
quartz is undesirable due to the abrasion it causes to the machinery (Ye
and Matsuoka, 1993d). Coarser impurities (generally quartz) are easily
separated by screening or classification while micron-sized impurities
require special treatments (Ediz et al., 2015; Mukai et al., 1974). The
authigenic ultrafine quartz grains (around 10 μm) are found in Late
Permian coal from Xuanwei, east Yunnan Province, Southwest China
(Zhao et al., 2016) and the Early Cretaceous Wulantuga coal, Inner
Mongolia, North China (Dai et al., 2012). For this reason, CSK is
discarded as a waste in some areas, and its accumulation is creating
new environmental problems.

⁎
Correspondence to: Geoffrey Evans, NIER, Callaghan University Drive, Callaghan, NSW 2308, Australia.
⁎⁎
Corresponding author.
E-mail addresses: geoffrey.evans@newcastle.edu.au (G. Evans), xgywl@cumt.edu.cn (G. Xie).

http://dx.doi.org/10.1016/j.clay.2017.04.020
Received 21 November 2016; Received in revised form 15 April 2017; Accepted 21 April 2017
Available online 28 April 2017
0169-1317/ © 2017 Elsevier B.V. All rights reserved.
X. Bu et al.
Froth flotation is well known as the most common process in
mineral separation to recover valuable minerals from gangue when
dealing with fine particles (Marion et al., 2015; Yang et al., 2010).
Flotation is strongly dependent on the degree of adsorption of collectors
onto the surface of the mineral. To determine whether the adsorption of
the collector is due to the electrostatic force or chemisorption, the
characteristics of the surface charge of the minerals is required
(Moudgil et al., 1987). The reason why it is difficult to separate quartz
from kaolin by flotation is that quartz has a similar surface charge to
kaolin (Kosmulski, 2009).
The flotation method for separating fine quartz from dickite (one of
the kaolin minerals) was developed by Mukai et al. (1974). They found
that dickite could float selectively from quartz by using dodecylammo-
nium acetate (DAA) as a collector in an acidic pH range. The reason for
the selectivity was thought to due to the hydrogen ions entering into the
interlayer of dickite instead of the DA+; and that the DA+ was adsorbed
on the dickite surface that was more negatively charged than that of the
quartz. Yoshikawa et al. (1989) separated dickite from quartz finer than
2 μm using a pressure type and a Denver type flotation cell. They
activated dickite with calcium chloride, and used sodium oleate as a
collector. Dickite has also been selectively floated from quartz at pH of
7 when the mixture of dickite and quartz (coarser than 5 μm) was
preconditioned in diluted HCl solution (Ye and Matsuoka, 1993a). In
the presence of inorganic electrolyte such as CaCl2 or KCl, the
decomposition of dickite during diluted HCl preconditioning is pro-
moted through an ion exchange reaction at short times. Good separa-
tion of dickite and quartz can be made for particles coarser than 2 μm,
while separation is still unsatisfactory for particles finer than 2 μm (Ye
and Matsuoka, 1993b). In order to improve the separation of dickite
from quartz finer than 2 μm, selective flocculation with the polymeric
flocculant, Separan AP30, was introduced to the flotation process which
includes preconditioning in diluted HCl solution containing CaCl2 (Ye
and Matsuoka, 1993c). In addition, it was found that dickite was
selectively flocculated and depressed by corn starch and satisfactory
separation between quartz and dickite was obtained (Ye and Matsuoka,
1993d).
In this study, the mineralogical composition of coal-series kaolin
from Xuzhou, Jiangsu Province of Eastern China was studied using X-
ray diffraction (XRD), scanning electron microscope (SEM), energy
dispersion spectrometer (EDS) and chemical analyses. The flotation
performance was investigated for pure mineral samples with conven-
tional depressants (hydrofluoric acid, sodium silicate and starch). In
order to meet the requirements for high quality of SiO2/Al2O3 weight
ratio, flotation experiments were also performed to effectively separate
quartz from dry rod mill output coal-series kaolin. The results from the
study highlight the potential benefits of applying flotation technology
to increase the utilization of coal-series kaolin deposits. In addition,
zeta potential measurements were employed to explain the mechanism
of the effect of reagents on minerals.
2. Experimental
2.1. Materials
Pure kaolin (< 10 μm) used in single flotation tests was obtained
from a kaolin mine of Suzhou, Jiangsu province, PR China. Pure quartz,
having a SiO2 grade higher than 99.8%, was purchased from Suqian
(Jiangsu province, PR China). In order to obtain a fine size fraction of
quartz the sample was passed through a hydrocyclone with a cut size of
10 μm. The hydrocyclone overflow was used directly for single mineral
flotation experiments.
The coal-series kaolin (CSK) sample, was supplied by Jiahe mine in
Xuzhou (Jiangsu province, PR China). For chemical analysis and X-ray
diffraction (XRD, Bruker D8 Advance, Germany) measurements, the
CSK sample was ground and milled to pass through a 320 mesh screen.
Polished thin-sections and block samples were prepared for scanning
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Applied Clay Science 143 (2017) 437–444
Table 1
Flotation reagents (analytical quality) used in this study.
Reagent name Molecular Reagent type Manufacturer
formula
DDA C12H25NH2 Collector Sinopharm Group
Hydrofluoric acid HF Depressant Zhongtai chemical
Sodium silicate Na2SiO3 Depressant Sinopharm Group
Starch (C6H10O5)n Depressant Sinopharm Group
Hydrochloric acid HCI pH modifier Aladdin Bio-Chem.
Tech.
Sodium hydroxide NaOH pH modifier Aladdin Bio-Chem.
Tech.
electron microscopic (SEM, FEI Quanta 250, US), coupled with an
EDAX energy dispersive X-ray spectrometer (EDS, JEOL Ltd., Japan),
observations. Following analysis, the CSK sample was crushed and
ground to a size fraction with 90% of the material being < 10 μm. The
material was then used for the flotation experiments.
Flotation reagents used in this study are shown in Table 1. DDA can
adsorb at the air/aqueous solution interface and obtain fine size
bubbles, which has been employed in kaolin flotation (Hu and Liu,
2003; Hu et al., 2005; Ma et al., 2009) and the reverse flotation of
quartz for the concentration of iron ores (Corona-Arroyo et al., 2015).
In this study, a stable froth can be obtained in the presence of DDA,
therefore the function of conventional frother reagent was replaced
with DDA.
2.2. Chemical analysis, XRD, SEM-EDS and zeta potential measurement
The CSK sample was initially characterized in terms of the miner-
alogical composition by chemical analysis and X-ray diffraction (XRD).
Chemical element analysis of the CSK was tested using chemical
titration method based on the Chinese standard GB/T 14563, 2008
(Liu et al., 2017; Zhu et al., 2014). X-ray fluorescence spectrometry
(XRF) was used to validate the chemical element results determined by
this chemical titration method. The difference of the oxides of mayor
elements between XRF and chemical titration techniques was ignorable.
XRD patterns were collected using a D/MAX-2500 pc powder diffract-
ometer equipped with Cu-Kα (λ = 1.54 Å) radiation which was gener-
ated at 40 kV and 40 mA in China University of Mining and Technol-
ogy. The samples for XRD analysis were measured from 5 to 80° (2θ)
with a step size of 0.02° (2θ) and a counting time of 0.2 s per step.
Morphology of minerals in the CSK sample were investigated using
and electron microscope equipped with an energy dispersive spectro-
meter (SEM-EDS) in China University of Mining and Technology. The
selected polished thin-sections and sample blocks were coated before
SEM observation. The SEM was operated with a beam voltage of
20.0 kV, working distance ~10 mm, and a spot-size of 5.5, while for the
Hitachi-S3400 X/I the accelerating voltage was 20 kV and the beam
current was 40–60 mA during SEM operation. The energy dispersive
spectroscopy (EDS) was taken at a vacuum of 10− 4 Pa using an
accelerated voltage of 20 kV to investigate the arrangement of the
present phases.
The zeta potential measurement was carried out by standard
procedures on a Brookhaven Zeta Plus Zeta potential meter. The sample
having 0.02% solid concentration was added into a 100 mL beaker. The
suspension was agitated for 2 min and transferred to the testing vessel,
after which the zeta potential measurement was made. The suspension
pH was modified with the addition of HCI and NaOH and measured by
REX Model PHS- 3C pH meter.
2.3. Single mineral flotation
Flotation tests were undertaken on both pure kaolin and quartz. All
flotation tests were conducted in a 1.5 L mechanical laboratory flota-
X. Bu et al. Applied Clay Science 143 (2017) 437–444

Fig. 2. Multi-stage flotation flowsheet of coal-series kaolin.

Fig. 1. Flowsheet of rougher flotation experiments.

calculated that 54.86% of the CSK is kaolinite. This method for the
tion machine operating with an air flowrate of 4.5 L/min. The mass of
estimate of the content of kaolinite has been confirmed by Wang et al.
solid particles used in each test was 30 g for both kaolin and quartz.
(2016). The SiO2/Al2O3 weight ratios of the CSK were significantly
These flotation tests were conducted in accordance with the flowsheet
higher than kaolinite, which is due to a large amount of quartz existed
shown in Fig. 1. Make-up water at the same pH was added as necessary
in this ore. Therefore, the removal of quartz from the CSK is vital for the
to maintain a constant pulp level. After conditioning, the air was then
industrial application of this deposit according to The Chinese national
turned on and the concentrate collected once all particles have under-
standard of kaolin (GB/T 14563-2008).
gone flotation. The collected concentrate and tailings were filtered,
For better understanding microstructure, phase compositions, and
dried and weighed to calculate the flotation recovery.
physical properties of the CSK sample, the microstructural evolution
was studied using SEM coupled with EDS.
2.4. Coal-series kaolin flotation
The SEM images in Fig. 4 show that a large number of particles in
nano-scale (< 30 μm) were embedded in the CSK sample. The corre-
Based on the single mineral flotation results, rougher flotation
sponding EDS mapping of Fig. 4A is shown in Fig. 5. Quartz particles
experiments were carried out using the ground and milled CSK sample
are indicated by the Si-rich and Al-poor regions in the images of Si and
with starch as a depressant. The reagent combinations tested in the
Al signals. The quartz particles are characterized by the Si-rich and Al-
rougher flotation experiments of the CSK sample are shown in Table 2.
poor regions. Quartz particle size measurements from SEM images were
Furthermore, a multi-stage flotation flowsheet (Fig. 2) was developed to
obtained using the Nano Measurer software. The resultant size dis-
promote the total mass recovery of coal-series kaolin with a given SiO2/
tribution of the quartz particles is given in Fig. 6, which indicates that
Al2O3 weight ratio according to the rougher flotation results. In order to
most of quartz particles were finer than 30 μm. Micro-crystalline quartz
quantify the performance of the removal of quartz from coal-series
grains (d90 = 15.8 μm) were found to be closely associated with the
kaolin, the grades of SiO2 and Al2O3 of the concentrate were tested
kaolin; and for this reason it was necessary to grind and mill the
according to the China Standard: GB/T 14563-2008 specification and
samples to liberate and separate quartz from the ore.
test method of kaolin clay.

3. Results and discussion 3.1.2. Electroacoustic zeta potential measurement

The zeta potential results of the CSK, pure kaolin and quartz used in
3.1. Characterization of coal-series kaolin this study are shown in Fig. 7. The results of pure kaolin indicated a
zero point of charge (zpc) of 2.51, which is in agreement with literature
3.1.1. Mineral components and dissemination characteristics zpc values of kaolinite of 2–4.5 (Kosmulski, 2009), 2.5–3.5 (Tschapek
The chemical analyses of the CSK samples are shown in Table 3. The et al., 1974) and 2.5–3.8 (Hu and Liu, 2003). As the solution pH
CSK sample was rich in SiO2 (56.72%) and poor in Fe2O3 (1.78%) and increased, the zeta potential of pure kaolin, pure quartz witnessed more
TiO2 (0.87%). The mineral components of the CSK according to XRD negative. Furthermore, the zeta potential of pure quartz revealed
results estimated by Jade 6.0 are reported in Fig. 3. The mineral significantly more negative in comparison with pure kaolin, which is
components of the CSK were kaolinite and quartz. Quartz was in agreement with the investigation by Yukselen-Aksoy and Kaya
considered as the main impurity mineral compared to muscovite (2011). However, Prasanphan and Nuntiya (2006) found that the
according to the results of chemical analyses and mineral determina- Ranong kaolin was higher negatively charged compared to quartz with
tion. Assumed that all of Al2O3 (21.67%) exist in kaolinite, it can be the pH range from 2 to 10.
Fig. 7 shown that pure quartz revealed the expected negative zeta
Table 2 potential across the investigated pH range, which also reported by
Conditions of coal-series kaolin in the rougher flotation process.
many researchers (Marion et al., 2015; Vidyadhar and Hanumantha,
Condition Starch (g/t) DDA (g/t) pH 2007; Yukselen-Aksoy and Kaya, 2011). In the literature, the zpc of
quartz values range from 1.7 to 2.6 according to the investigations by
1 0 300 3 Duarte and Grano (2007), Kosmulski et al. (2002), Prasanphan and
2 40 300 3
3 80 300 3
Nuntiya (2006) and Xu et al. (2003). These differences may arise from
4 120 300 3 the difference in production, store, and surface properties of the quartz
5 160 300 3 powder (Xu et al., 2003).
6 120 100 3 The zeta potential of the CSK was less negative compared to pure
7 120 200 3
quartz, while more negative than pure kaolin. The similar finding was
8 120 300 3
9 120 400 3 also observed in the investigation of the mixture of quartz and Ranong
kaolin by Prasanphan and Nuntiya (2006). Permanent negative charge

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X. Bu et al. Applied Clay Science 143 (2017) 437–444

Table 3
Oxide composition (%) of the coal-series kaolin and kaolinite.

Sample SiO2 Al2O3 CaO MgO K2O Na2O Fe2O3 TiO2 SO3 LOI

Kaolinite 46.54 39.50 – – – – – – – 13.96

CSK 56.72 21.67 0.28 0.32 1.80 0.37 1.78 0.87 0.45 14.13

3.2. Single mineral flotation

3.2.1. Effect of DDA and pH

Fig. 3. XRD patterns of the CSK sample with respect to mineral identification.
of kaolin is higher than that of quartz due to the isomorphic substitution
or structure defects (Taubaso et al., 2004).
Pure kaolin and pure quartz have the similar surface charge, thus it
is difficult for the selective separation of kaolin from quartz using an
amine collector relying on electrostatic attraction as the basic mechan-
ism of adsorption.
Results from the flotation of pure kaolin and quartz using DDA as
collector are shown in Figs. 8 and 9. Effective separation between
kaolin and quartz mineral was possible using DDA as collector in acidic
and neutral media. In acidic and neutral media, pure kaolin was found
to have a moderate recovery but then decreased sharply with further
increases in pH. The flotation behavior of pure kaolin near pH 10 is in
good agreement with the solubility limit of DDA in alkaline medium
(Yoon and Ravishankar, 1996). Based on quantum chemistry calcula-
tions, Hu et al. (2005) proposed that the interaction between DDA and
−
the (001) plane of kaolinite is stronger than that at the (001) alumina
−
plane due to the differences in the structure at the (001) and (001)
planes. Therefore, the high flotation recovery of kaolin can be due to
the kaolinite aggregates hydrophobic results from the self-aggregation
−
between (001) faces and the edge planes and the adsorption of DDA at
the silica (001) plane make in acidic solution. In alkaline solution, the
kaolinite particles are dispersed. In the presence of DDA, hydrophobic
aggregation appears to occur in alkaline solution between the (001)
−
planes due to adsorbed DDA, and thus the hydrophilic (001) faces are
exposed and flotation is not achieved. This can explain the pure kaolin
flotation results observed in Fig. 8.
Quartz is negatively charged above its point of zero charge that

Fig. 4. Microscopic observations of the CSK sample (SEM).

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X. Bu et al. Applied Clay Science 143 (2017) 437–444

Fig. 5. EDS mapping images of Fig. 4A (Left: Si; Right: Al).

Fig. 8. Single mineral flotation results for single mineral flotation as a function of pH
(100 g/t DDA, without depressant).

Fig. 6. Size distribution of quartz particles of the CSK sample.

Fig. 9. Effect of DDA dosage on single mineral flotation (pH = 3).

Fig. 7. Zeta potential trend of pure kaolin, pure quartz and CSK.

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X. Bu et al. Applied Clay Science 143 (2017) 437–444

occurs at pH = 2–3. The cationic collector (DDA) participates in cation Table 4

exchange reactions in which dissolved ions replace ions bound by Zeta potentials of quartz with starch as depressant (50 g/t starch).
negatively charged sites on mineral particles (Rao et al., 1980). Based
Mineral Quartz
on the classical explanation for cationic flotation of oxides and silicates,
good flotation with a cationic collector in the pH region where the Without reagent Starch
mineral surface is negatively charged should be expected. Stronger
ζ/mV − 32.63 − 2.68
flotation of quartz was observed in alkaline and neutral medium in
comparison to acidic medium, since the surface charge of oxides grows
more negative as pH increases (Smith and Scott, 1990). Single mineral Table 5
flotation results for quartz shown in Fig. 8 are in agreement with the Effect of starch dosage on coal-series kaolin flotation.
investigation by Vidyadhar et al. (2014). Flotation recovery of pure
kaolin decreased with increasing pH, which is opposite to that for Starch Total mass Grade (%) Recovery SiO2/Al2O3
dosage (g/t) recovery (%) (Al2O3) (%) weight ratio
cationic flotation of quartz mineral where recovery generally increases
SiO2 Al2O3
with increases in pH. Compared to pure kaolin, quartz was clearly
depressed in the acidic pulp. 0 69.74 51.71 28.86 92.87 1.79
The effect of DDA dosage on single mineral flotation at pH = 3 is 40 64.62 49.32 30.25 90.20 1.63
80 60.40 47.67 32.04 89.32 1.49
shown in Fig. 9. Recoveries of both pure kaolin and quartz increased
120 57.47 45.89 33.30 88.31 1.38
with increasing collector concentration. However, the increase was 160 57.47 45.53 33.30 88.31 1.37
much less significant for the dosage beyond 300 g/t, suggesting that
flotation recovery was not sensitive to surface coverage of collector on
the particles beyond this point. Flotation recovery of pure kaolin was Table 6
significantly higher than that of quartz, with the difference not being Effect of DDA dosage on coal-series kaolin flotation.
sensitive to DDA dosage.
DDA dosage Total mass Grade (%) Recovery SiO2/Al2O3
(g/t) recovery (%) (Al2O3) (%) weight ratio
SiO2 Al2O3
3.2.2. Effect of depressant
The addition of a depressant is often useful as it adsorbs onto the 100 37.26 44.16 35.09 60.33 1.26
gangue minerals and prevents their recovery (Kulkarni and 200 49.63 45.27 34.16 78.24 1.33
300 57.47 45.89 33.30 88.31 1.38
Somasundaran, 1980). The effect of increasing dosage of conventional
400 60.81 46.59 32.74 91.87 1.42
depressants in suppressing quartz particles was investigated. Conven-
tional depressants tested including hydrofluoric acid (HF), sodium
silicate and starch. All flotation experiments were conducted at Table 7
conditioning pH = 3 and 300 g/t DDA. Flotation results of pure kaolin Multi-stage flotation flowsheet results of coal-series kaolin.
and quartz with all three depressants are shown in Fig. 10.
Name Total mass Grade (%) Recovery SiO2/Al2O3
Hydrofluoric acid has been used to activate feldspar prior to its
recovery (%) (Al2O3) (%) weight ratio
amine collector flotation separation from quartz material. The separa- SiO2 Al2O3
tion was achieved at low pH where the zeta-potential of the feldspar
remained negative while that of the quartz became close to neutral Concentrate 46.55 44.72 34.83 74.68 1.28
Middling 22.77 60.47 18.87 19.79 3.20
(Peres et al., 2007). Quartz recovery decreased with increasing HF
Tailings 30.68 72.90 6.28 8.88 11.61
dosage up to 100 g/t and thereafter remained constant. HF dosage had
no apparent effect on the pure kaolin recovery; and on this basis it can
be concluded that HF addition had a beneficial effect on depressing the Sodium silicate is a known dispersant/depressant for silicate
unwanted recovery of quartz particles. However, hydrofluoric acid is an minerals, slime and iron oxides (Li et al., 2005; Satur et al., 2016).
industrial chemical that poses challenges with respect to health, safety The addition of sodium silicate resulted in a reduction of pure kaolin
and environment. recovery from 85% to approximately 75%. Similarly, quartz recovery
decreased from 21% to approximately 14%. Recoveries of pure kaolin
and quartz remained constant when the sodium silicate dosage was
increased from 50 to 400 g/t. Sodium silicate, therefore, would most
likely be a non-selective depressant the combined kaolin-quartz system.
Starch is a known depressant for hematite, weathered silicates, and
carbonaceous matter (Weng et al., 2013). As shown in Fig. 10, starch
had no effect on the pure kaolin recovery. Conversely, quartz recovery
was reduced from 20% to 3% when the starch dosage was increased 0
to 20 g/t; with quartz recovery remaining constant beyond this dosage.
The influence of starch at 300 g/t DDA and pH 3.0 on the zeta
potentials of quartz and kaolin is presented in Table 4. The zeta
potential of quartz dropped from − 32.63 mV to − 2.68 mV after
conditioning with starch. This is probably related to a partial conceal-
ment of the quartz surface charges by very large adsorbed starch
molecules through hydrogen bonding, which can explain the depression
of quartz.
Starch can be an effective depressant for quartz recovery whilst at
the same time appearing to have no deleterious influence on kaolin
recovery. Unlike the other effective depressant (HF), starch is an
environmentally benign reagent. Therefore starch was chosen for
Fig. 10. Effect of depressant dosage on pure mineral floatation. further flotation investigation using the coal-series kaolin material.

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X. Bu et al.
3.3. Coal-series kaolin (CSK) flotation
The CSK flotation experiments on the ground and milled feed were
carried out using starch as depressant and DDA as the collector. Total
mass recovery, Al2O3 recovery, and SiO2/Al2O3 weight ratio of the
concentrate were used to evaluate the flotation performance for
separating the fine quartz from the CSK sample.
Effect of starch dosage (with 300 g/t DDA dosage) on flotation
recovery is shown in Table 5. It can be seen that the SiO2/Al2O3 weight
ratio decreased from 1.63 to 1.37 as the starch dosage was increased
from 0 to 160 g/t, indicating that the starch was effective in depressing
quartz flotation. However, it can be seen that at the same time the
recovery of Al2O3 decreased from 90.20% to 88.31%, which revealed
that part of kaolin was reporting to the tailings with the increase in
starch dosage.
Effect of DDA dosage (with 160 g/t starch dosage) on flotation
recovery is shown in Table 6. It can be seen that increasing DDA dosage
resulted in increases in total mass and Al2O3 recoveries as well as the
SiO2/Al2O3 weight ratio.
From the results given in Tables 5 and Table 6, at a relatively low
DDA dosage and high starch dosage the required product requirement
of SiO2/Al2O3 weight ratio of < 1.29 was obtained in the rougher
flotation process, but at the cost of a large loss of kaolin into the
gangue. Consequently, a multi-stage flotation flowsheet (Fig. 2) was
designed to reduce those kaolin losses whilst still achieving the required
SiO2/Al2O3 weight ratio. The results of the multi-stage flotation
experiments are shown in Table 7. It can be seen that a SiO2/Al2O3
weight ratio of 1.26 was able to be achieved within a kaolin recovery of
46.55%, which is quite acceptable.
CSK which is discard as a waste (gangue) in coal preparation plants
is easy to obtain for the proposed method. The reagents and multi-stage
flotation circuit used in this study are widely acceptable in mineral
processing industry. However, a large amount of energy is consumed to
liberate kaolin minerals from purities in the comminution and grinding
of raw ores. However, it is desirable for the beneficiation of CSK with
the depletion of other kaolin deposits, the increase in kaolin demands
and the rising concerns of environment pollution resulted from the
accumulation of CSK. Furthermore, some special facilities and policies
provided by the government can also enhance the large scale applica-
tion of CSK.
4. Conclusions
This work investigated the separation of fine quartz from a coal-
series kaolin sample (Xuzhou, Jiangsu Province of Eastern China). The
mineralogical, morphological, chemical characteristics of the coal-
series kaolin were analyzed in order to liberate quartz from kaolin.
Single mineral flotation tests of pure kaolin and quartz was carried out
to evaluate flotation responses in the presence of an amine collector
(DDA) and three depressants (HF, sodium silicate and starch). The
results were then applied to the flotation tests performed on the ground
and milled coal-series kaolin. It was found that:
1. Micro-crystalline quartz grains (d90 = 15.8 μm) were the major
impurity mineral of this coal-series sample. At this size range the
kaolin could not be separated from the quartz by screening or other
types of classification methods.
2. Selective flotation separation of the pure kaolin from the quartz
contaminant was possible using DDA as the collector in acidic
media. Starch, an environment-friendly material, was found to be an
effective depressant for the quartz material. This is due to a partial
concealment of the quartz surface charges by very large adsorbed
starch molecules through hydrogen bonding according to the zeta
potential results.
3. With multi-stage flotation total mass recovery of 46.55% kaolin was
able to be achieved with the required SiO2/Al2O3 weight ratio
443
Applied Clay Science 143 (2017) 437–444
of < 1.26.
Acknowledgement
This work was supported by the Fundamental Research Funds for
the Central Universities (Grants No. 2017BSCXA07).
References
Corona-Arroyo, M.A., López-Valdivieso, A., Laskowski, J.S., Encinas-Oropesa, A., 2015.
Effect of frothers and dodecylamine on bubble size and gas holdup in a downflow
column. Miner. Eng. 81, 109–115.
Dai, S., Wang, X., Seredin, V.V., Hower, J.C., Ward, C.R., O'Keefe, J.M., Xue, W., 2012.
Petrology, mineralogy, and geochemistry of the Ge-rich coal from the Wulantuga Ge
ore deposit, Inner Mongolia, China: new data and genetic implications. Int. J. Coal
Geol. 90, 72–99.
Duarte, A.C.P., Grano, S.R., 2007. Mechanism for the recovery of silicate gangue minerals
in the flotation of ultrafine sphalerite. Miner. Eng. 20, 766–775.
Ediz, N., Tatar, I., Aydin, A., 2015. Pre-concentration and flotation of alunitic kaolin and
its possible use in ceramic tile industry. Physicochem. Prob. Min. Proces. 51,
213–231.
Hu, Y., Liu, X., 2003. Chemical composition and surface property of kaolins. Miner. Eng.
16, 1279–1284.
Hu, Y., Wei, S., Hao, J., Miller, J.D., Fa, K., 2005. The anomalous behavior of kaolinite
flotation with dodecyl amine collector as explained from crystal structure
considerations. Int. J. Miner. Process. 76, 163–172.
Jepson, B.W., 1988. Structural iron in kaolinites and in associated ancillary minerals. In:
Stucki, M.J. (Ed.), Iron in Soils and Clay. Springer Netherlands, Reidel, Dordrecht, pp.
467–536.
Jones, M.L., Kalmanovitch, D.P., Steadman, E.N., Zygarlicke, C.J., Benson, S.A., 1992.
Application of SEM techniques to the characterization of coal and coal ash products.
In: Meuzelaar, H.L.C. (Ed.), Advances in Coal Spectroscopy. Plenum Press, New York,
pp. 1–27.
Kosmulski, M., 2009. Surface Charging and Points of zero Charge. CRC Press.
Kosmulski, M., Maczka, E., Janusz, W., Rosenholm, J.B., 2002. Multiinstrument study of
the electrophoretic mobility of quartz. J. Colloid Interface Sci. 250, 99–103.
Kulkarni, R.D., Somasundaran, P., 1980. Flotation chemistry of hematite/oleate system.
Colloids Surf. 1, 387–405.
Li, H., Zhou, Z.A., Xu, Z., Masliyah, J.H., 2005. Role of acidified sodium silicate in low
temperature bitumen extraction from poor-processing oil sand ores. Ind. Eng. Chem.
Res. 44, 4753–4761.
Liu, Y., Lei, S., Huang, T., Ji, M., Li, Y., Fan, Y., 2017. Research on mineralogy and
flotation for coal-series kaolin. Appl. Clay Sci. 136, 37–42.
Ma, X., Bruckard, W.J., Holmes, R., 2009. Effect of collector, pH and ionic strength on the
cationic flotation of kaolinite. Int. J. Miner. Process. 93, 54–58.
Marion, C., Jordens, A., McCarthy, S., Grammatikopoulos, T., Waters, K.E., 2015. An
investigation into the flotation of muscovite with an amine collector and calcium
lignin sulfonate depressant. Sep. Purif. Technol. 149, 216–227.
Mohammadi, T., Pak, A., 2003. Effect of calcination temperature of kaolin as a support for
zeolite membranes. Sep. Purif. Technol. 30, 241–249.
Moudgil, B.M., Soto, H., Somasundaran, P., 1987. Adsorption of surfactants on minerals.
In: Somasundaran, P., Moudgil, B.M. (Eds.), Reagents in Mineral Technology. Marcel
Dekker, Inc., New York, pp. 79–104.
Mukai, M., Matsuoka, I., Shimoiizaka, J., 1974. Fundamental study on the removal of
silica from kaolin mineral by amine flotation. J. Min. Metall. Inst. Jpn. 90, 487–492.
Murray, H.H., 1963. Industrial applications of kaolin. Clay Clay Miner. 10, 291–293.
Murray, H.H., 2000. Traditional and new applications for kaolin, smectite, and
palygorskite: a general overview. Appl. Clay Sci. 17, 207–221.
Newns, A., Pascoe, R.D., 2002. Influence of path length and slurry velocity on the removal
of iron from kaolin using a high gradient magnetic separator. Miner. Eng. 15,
465–467.
Peres, A.E.C., Araujo, A.C., El-Shall, H., Zhang, P., Abdel-Khalek, N.A., 2007. Plant
practice: nonsulfide minerals. In: Fuerstenau, M.C., Jameson, G., Yoon, R.-H. (Eds.),
Froth Flotation – A Century of Innovation. Society for Mining, Metallurgy, and
Exploration, Inc. (SME), Colorado, pp. 845–868.
Prasanphan, S., Nuntiya, A., 2006. Electrokinetic properties of kaolins, sodium feldspar
and quartz. Chiang Mai J. Sci. 33, 183–190.
Rafatullah, M., Sulaiman, O., Hashim, R., Ahmad, A., 2010. Adsorption of methylene blue
on low-cost adsorbents: a review. J. Hazard. Mater. 177, 70–80.
Raghavan, P., Chandrasekhar, S., Vogt, V., Gock, E., 2004. Separation of titanoferrous
impurities from kaolin by high shear pretreatment and froth flotation. Appl. Clay Sci.
25, 111–120.
Rao, M., Odom, D.G., Oro, J., 1980. Clays in prebiological chemistry. J. Mol. Evol. 15,
317–331.
Saikia, J.N., Bharali, J.D., Sengupta, P., Bordoloi, D., Goswamee, L.R., Saikia, C.P.,
Borthakur, C.P., 2003. Characterization, beneficiation and utilization of a kaolinite
clay from Assam, India. Appl. Clay Sci. 24, 93–103.
Satur, J.V., Calabia, B.P., Hoshino, M., Morita, S., Seo, Y., Kon, Y., Takagi, A.T.,
Watanabe, B.Y., Mutele, L., Foya, S., 2016. Flotation of rare earth minerals from
silicate–hematite ore using tall oil fatty acid collector. Miner. Eng. 89.
Smith, R.W., Scott, J.L., 1990. Mechanisms of dodecylamine flotation of quartz. Min.
Proces. Extr. Metall. Rev. 7, 81–94.
Taubaso, C., Afonso, M.D.S., Sánchez, R.M.T., 2004. Modelling soil surface charge density
X. Bu et al.
using mineral composition. Geoderma 121, 123–133.
Tschapek, M., Tcheichvili, L., Wasowski, C., 1974. The Point of zero Change of Kaolinite
and Si O2 + Al2 O3 Mixtures .
Vidyadhar, A., Hanumantha, R.K., 2007. Adsorption mechanism of mixed cationic/
anionic collectors in feldspar-quartz flotation system. J. Colloid Interface Sci. 306,
195–204.
Vidyadhar, A., Kumari, N., Bhagat, R.P., 2014. Adsorption mechanism of mixed cationic/
anionic collectors in quartz–hematite flotation system. Miner. Process. Extr. Metall.
Rev. 35, 117–125.
Wang, Y., Liang, H., Chang, Q., Zhang, X., 2016. Separation of kaolinite from ion-
adsorption rare earth tailings in Southern China and iron removal treatment. J.
Miner. Mater. Charact. Eng. 40, 40–47.
Weng, X., Mei, G., Zhao, T., Zhu, Y., 2013. Utilization of novel ester-containing
quaternary ammonium surfactant as cationic collector for iron ore flotation. Sep.
Purif. Technol. 103, 187–194.
Wilson, I.R., 2004. Kaolin and halloysite deposits of China. Clay Miner. 39, 1–15.
Xu, G., Zhang, J., Song, G., 2003. Effect of complexation on the zeta potential of silica
powder. Powder Technol. 134, 218–222.
Yang, Y., Li, Y., Zhang, Y.M., Liang, D.W., 2010. Applying hybrid coagulants and
polyacrylamide flocculants in the treatment of high-phosphorus hematite flotation
wastewater (HHFW): optimization through response surface methodology. Sep. Purif.
Technol. 76, 72–78.
Ye, H., Matsuoka, I., 1993a. Oleate flotation of dickite from quartz with diluted HCl
444
Applied Clay Science 143 (2017) 437–444
preconditioning. I. Effect of HCl preconditioning. Int. J. Miner. Process. 40, 83–98.
Ye, H., Matsuoka, I., 1993b. Oleate flotation of dickite from quartz with diluted HCl
preconditioning. II. Effect of CaCl2 and KC. Int. J. Miner. Process. 40, 99–109.
Ye, H., Matsuoka, I., 1993c. Oleate flotation of dickite from quartz with diluted HCl
preconditioning. III. Improvement in fine particle flotation by selective flocculation.
Int. J. Miner. Process. 40, 111–121.
Ye, H., Matsuoka, I., 1993d. Reverse flotation of fine quartz from dickite with oleate. Int.
J. Miner. Process. 40, 123–136.
Yoon, R.H., Ravishankar, S.A., 1996. Long-range hydrophobic forces between mica
surfaces in alkaline dodecylammonium chloride solutions. J. Colloid Interface Sci.
179, 403–411.
Yoshikawa, I., Nozawa, M., Matsuoka, I., Shimoiizaka, J., 1989. The separation of fine
Dickite and quartz by pressure type flotation. J. Min. Metall. Inst. Jpn. 105, 311–314.
Yukselen-Aksoy, Y., Kaya, A., 2011. A study of factors affecting on the zeta potential of
kaolinite and quartz powder. Environ. Earth Sci. 62, 697–705.
Zhao, L., Dai, S., Graham, I.T., Wang, P., 2016. Clay mineralogy of coal-hosted Nb-Zr-
REE-Ga mineralized beds from Late Permian Strata, Eastern Yunnan, SW China:
implications for paleotemperature and origin of the micro-quartz. Fortschr. Mineral.
6, 45.
Zhu, P.W., Zeng, W.Q., Xu, X.L., Cheng, L.M., Jiang, X., Shi, Z.L., 2014. Influence of acid
leaching and calcination on iron removal of coal kaolin. Int. J. Miner. Metall. Mater.
21, 317–325.