Mining, Metallurgy & Exploration

https://doi.org/10.1007/s42461-018-0033-7

Efficient Separation of Trace Muscovite within the Surface/Interface

of Quartz Grains from a Hydrothermal Deposit by Oxidizing Calcination
and Catalytic Pressure Leaching
Zhenyu Pei 1 & Min Lin 2 & Yu Meng 2 & Hang Qiu 2 & Xun Zhang 3 & Shaomin Lei 1 & Yubiao Li 1,4 & Andrea R. Gerson 4

Received: 11 September 2018 / Accepted: 3 December 2018

# The Society for Mining, Metallurgy & Exploration 2018

Abstract
Efficient separation of trace muscovite from the surface/interface of quartz grains was accomplished during oxidizing calcination and
catalytic pressure leaching of the hydrothermal quartz. Experimental results suggest that 98.97% or more of the muscovite was
separated when quartz sand was calcined at 900 °C for 5 h and then leached by hydrochloric acid and ammonium chloride solutions
as substitutes for leaching agents containing fluorides. The chemical processing techniques show high selectivity in purifying quartz
sand by transforming mineral muscovite into active structures during oxidizing calcination, and then dissolving the active substances
during catalytic pressure leaching.

Keywords Hydrothermal quartz . Trace muscovite . Surface/interface . Separation . Oxidizing calcination . Pressure leaching

1 Introduction applications include manufacturing of crucibles and the produc-

The origin of quartz processing can be traced back to the work of
Scott and Smith [1, 2]. Since then, many studies have been
carried out in the search for suitable substitutes for high-purity
crystal quartz [3–5]. Hydrothermal quartz, as a high-grade SiO2
resource, has recently attracted much attention. It is considered
the best potential Si source as a substitute for crystal quartz,
which is widely applied in modern industry.
High-grade quartz is an important raw material used to pro-
duce alkali-free glass and fused silica, which are commonly used
in several modern technology fields [6–8]. The major
* Min Lin
13297013624@163.com
* Yubiao Li
Yubiao.Li@whut.edu.cn
1
School of Resources and Environmental Engineering, Wuhan
University of Technology, Wuhan 430070, People’s Republic of
China
2 to the silicon-oxygen structure [21, 22]. The use of fluoric
Wuhan BOE Optoelectronics Technology Co., Ltd., Wuhan 430040,
People’s Republic of China
3 serious environmental pollution, although they can effec-
Jiangsu Kaida Quartz Co., Ltd., Xinyi 221400, People’s Republic of
China
4 interface of quartz grains [23–25]. In addition, the selec-
School of Natural and Built Environments, University of South
Australia, Mawson Lakes, SA 5095, Australia
tion of transparent bulbs for UV light-induced water purification
[9–11]. Adequate properties including chemical purity, optical
transparency and radiation resistance are necessary for alkali-
free glass and silica glass employed in such applications [6].
Some research shows that the efficiency of solar silicon process-
ing is decreased by crucibles with less pure fused silica [9, 12,
13]. Impurities such as Al, Fe, K and Mg are able to markedly
reduce transparency and radiation resistance of quartz wares,
resulting in reduced performance when quartz containing these
impurities is used, such as in light bulbs [14–16].
Industrial minerals such as hydrothermal quartz usually
contain some gangue muscovite [17] and are indeed contam-
inated by small amounts of Al (200–400 ppm) and K (100–
200 ppm) for many major hydrothermal deposits. Thus, the
removal of trace and fine-grain mica minerals is a key problem
faced by the producers of such industrial minerals. The main
processing techniques for quartz, including fine-particle flota-
tion and acid leaching, have been adequately developed in
recent years [18–20], but fluorides are still widely applied in
these processing techniques because of their efficient damage
reagents, especially hydrofluoric acid, commonly leads to
tively remove aluminosilicate minerals from the surface/
tivity of some enhanced leaching processes using hydrogen
 Mining, Metallurgy & Exploration

fluoride (HF) is so low that the particle size of quartz sand

may be sharply reduced during the processes as gangue
minerals are removed [26, 27]. Furthermore, most
fluorine-free processing techniques are barely satisfactory
in purification efficiency and rate.
Metallurgical techniques including oxidizing calcination
and pressure leaching have shown great effects in separating
fluid and mineral impurities from hydrothermal quartz [28].
Oxidizing calcination can remove fluid inclusions and trans-
form mineral impurities into their active phases, after which
the active substances can be efficiently dissolved by pressure
leaching. More importantly, pressure leaching using mixed
leaching agents containing acid and inorganic salt has demon-
strated distinctive effects on dissolving muscovite in mica
shale [29]. Lin et al. proposed a novel leaching solution
consisting of hydrochloric acid and ammonium chloride that
may efficiently dissolve mineral impurities while avoiding the
introduction of some metal cations into the environment [28].
Based on previous research [30–32], the objective of this
study is to investigate the effects of metallurgical techniques Fig. 1 Leaching experimental apparatus: PPL-para polystyrene
(oxidizing calcination and pressure leaching) on purifying
quartz sand, and to thoroughly elucidate the separation mech-
anisms of trace muscovite from hydrothermal quartz when process is to destroy the crystal structures of gangue minerals
using HCl-NH4Cl solution. The research is focused on ana- and increase their exposure probability [30, 31].
lyzing the dissolution behaviors of the trace muscovite from
the surface/interface of quartz grains during pressure leaching.
2.3 Pressure Leaching

All leaching tests of calcined quartz sand were conducted in a

2 Experimental 100 cm3 para polystyrene jar in a reaction kettle. The experi-
mental apparatus (Fig. 1) containing quartz sand and leaching
2.1 Quartz Ore solutions was heated by hot air in an electro-thermal hot-air
drying oven (DHG-9075A). In general, the liquid/solid ratio is
Quartz samples including bulk quartz and quartz sand were 10 cm3/g (5 g of quartz sand and 50 cm3 of leaching solution).
obtained from a hydrothermal vein quartz deposit located in After leaching, the reaction kettle was rapidly cooled by water.
Qichun County of Hubei Province, China [30]. Bulk quartz Leached quartz sand was collected for content analyses of Al
was sliced and polished into quartz sections for microprobe and K after ultrasonic cleaning.
analysis. The mineral phases and optical characteristics of
gangue minerals in bulk quartz and quartz sand, respectively, (1) HCl-HF-NH4Cl solutions were used to leach calcined
were investigated using a polarizing microscope (DMLP). quartz sand in single-factor tests for NH4Cl concentra-
The content of trace impurity elements in quartz sand was tion (0.0, 0.2, 0.4, 0.6, 0.8, 1.0 mol/dm3), leaching
analyzed by inductively coupled plasma-optical emission
spectroscopy/mass spectrometry (ICP-OES/MS) after HF at-
tack. The particle sizes and specific areas of quartz sand sam- Table 1 Factors and levels investigated in leaching tests
ples were ascertained by means of a laser granulometer
Factor Unit Level
(BT9300S).
1 2 3
2.2 Oxidizing Calcination A HCl mol/dm3 0.2 0.5 0.8
3
B HF mol/dm 0.0 0.1 0.2
Quartz sand samples were calcined at 900 °C for 5 h in a C Leaching time h 2 3 4
muffle furnace (KSY-12-16A). The calcined quartz sand was D NH4Cl mol/dm3 0.4 0.8 1.2
rapidly poured into ultrapure water (18.2 MΩ·CM) and then
dried for leaching experiments. The purpose of the calcination L/S ratio 10 cm3 /g, leaching temperature 280 °C
Mining, Metallurgy & Exploration
Fig. 2 Relationship of quartz grains at crossed and polarized light (XPL)
temperature (200, 220, 240, 260, 280 °C) and liquid/
solid ratio (1, 4, 7, 10, 13, 16 cm3/g). The single-factor
tests were used to evaluate the effect of NH4Cl on im-
proving leaching efficiency.
(2) An orthogonal experiment was performed to evaluate the
influence of HCl, HF, NH4Cl and leaching time on the
content of Al and K. Table 1 shows the factors and levels
investigated in the orthogonal experiment. Through an
optimization process, optimal conditions were obtained
when using HCl-NH4Cl solution as a substitute for HCl-
HF-NH4Cl solutions. Finally, further testing of leaching
time (4, 5, 6, 7, 8 h) and contrast testing with and without
ammonium chloride were completed.
2.4 Analyses of Structure and Content
Muscovite in calcined quartz sand was observed by scan-
ning electron microscopy (SEM, JSM-IT300). The elemen-
tal composition of the main associated minerals was
ascertained by X–ray energy-dispersive spectrometry
Fig. 3 Main gangue minerals in
Qichun quartz: a fine-grained
muscovite (XPL), b hematite at
reflected, crossed and polarized
light (RXPL). M - muscovite, H -
hematite
(EDS). Muscovites in quartz ore and calcined quartz sand
were observed by transmission electron microscopy (TEM,
JEM-2100F). Quartz samples were dissolved by pressure
reaction for elemental content analysis [30]. The solutions
from sample dissolution were analyzed by ICP-OES
(Prodigy7) and ICP-MS (iCAP-Qc). Based on the method
described by Lin et al., the relative standard deviation for
the method is less than 3% as a whole [30, 32].
The resolution ratio for SEM at the secondary electron
image was 3.0 nm, image magnification ×5 to ×300,000, ac-
celeration voltage 0.3–30 kV, spot diameter 5.0–10 nm.
Secondary and backscattered electron images were obtained
at 20.0 kV acceleration voltage, 16.2–16.6 mm working dis-
tance and 1 μm spot size for the secondary electron image, and
11.3 mm for the backscattered electron image. The analytical
precision of EDS was as follows: analysis element: 5B–92 U,
2–3% for common element, detection limit: 0.1–0.5 wt.%.
Resolution ratio of TEM, 0.20 nm; image magnification,
×50 to ×11,000,000; acceleration voltage, 160–200 kV; min-
imum spot diameter, 0.5 nm. Transmission electron micro-
graphs are obtained at 200 kV acceleration voltage and
1 mm Cs. EDS, 10−14–10−21 g analytical sensitivity; analysis
element, 5B–92 U.
Wavelength coverage of ICP-OES, 165–1100 nm; optical
resolution, 0.007 nm at 200 nm; relative standard deviation, <
2%. Mass spectrum of ICP-MS, 4–290 amu; sensitivity, > 150
Mcps·ppm−1 for common elements; detection limit, < 0.1 ppt
for common element; relative standard deviation, < 2% in
short time; < 3% in long time.
2.5 Separation Efficiency
The optimal separation efficiency of muscovite can be approx-
imated by calculating the extraction rate of K in quartz con-
centrate, although little of the removed K is from the quartz
lattice [30, 33]. But it is best to use the content of Al and K to
evaluate the removal effect of muscovite during single-factor
tests, because K in the interlayer is commonly leached prior to
Al in layer silicate minerals [31].
 Mining, Metallurgy & Exploration

Table 2 Content of main impurity elements in quartz sand (μg·g−1)

Element Al K Fe Mg Na B Ti Ca P Zr S Others In Total

Content 352.7 118.1 61.22 11.80 13.45 10.79 8.341 8.050 15.51 6.463 5.644 6.937 619.0

η ¼ ηðKÞ 3.2 Quartz Purification

where η is the separation efficiency of muscovite, %, η(K) is
the extraction rate of K on the optimal leaching condition, %.
3 Results
3.1 Mineralogy Analysis
The Qichun quartz is from a hydrothermal vein deposit widely
distributed around Qichun County [30]. Coarse quartz grains
are commonly surrounded by some fine quartz grains (Fig. 2).
The size of the crystalline grains ranges from 400 to 1000 μm.
Polarizing microscopy analysis shows that the main
gangue minerals in the quartz ore are muscovite and hema-
tite (Fig. 3). The muscovite, as a silicate mineral, common-
ly contains some Al and K. As shown in Fig. 3, the mus-
covite is widely distributed around the quartz grain bound-
ary. Feldspar is not observed on detailed mineralogical
study. Muscovite is the main associated mineral potentially
containing Al and K in the quartz. Hence, the content of Al
and K can be used to calculate separation efficiency of
muscovite from the quartz.
Table 2 shows the content of the main impurity elements in
quartz sand. The Al and K content is 352.7 μg·g−1 and
118.1 μg·g−1, respectively.
The effects of processing parameters including NH 4Cl
concentration, leaching temperature, liquid/solid ratio
and leaching time on quartz purification have been
discussed in detail.
3.2.1 Effects of NH4Cl Concentration on Elemental Content
Figure 4 shows the content of Al and K at different NH4Cl
concentrations at 200 °C leaching temperature, 10 cm3/g
liquid/solid ratio, 0.8 mol/dm 3 HCl concentration, and
0.2 mol/dm3 HF concentration. The Al and K content was
reduced from 57.53 and 4.005 μg·g −1 to 48.36 and
3.666 μg·g−1, respectively, when the NH4Cl concentration
was increased from 0.0 mol/dm3 to 0.4 mol/dm3, whereas
their content increased with increased NH4Cl concentration
from 0.4 mol/dm3 to 1.0 mol/dm3.
3.2.2 Effects of Leaching Temperature on Elemental Content
The influence of leaching temperature on the content of Al
and K is shown in Fig. 5. The results reveal an obvious de-
crease in Al and K content with leaching temperature. At
280 °C, the content of Al and K was reduced to 47.12 and
1.979 μg·g − 1 , respectively. The higher-temperature

Fig. 4 Effects of NH4Cl on

content of Al and K in quartz sand
samples: leaching temperature,
200 °C; L/S ratio, 10 cm3/g; HCl
concentration, 0.8 mol/dm3; HF
concentration, 0.2 mol/dm3;
leaching time, 3 h
Mining, Metallurgy & Exploration

Fig. 5 Effects of leaching

temperature on content of Al and
K: L/S ratio, 10 cm3/g; NH4Cl
concentration, 0.4 mol/dm3; HCl
concentration, 0.8 mol/dm3; HF
concentration, 0.2 mol/dm3;
leaching time, 3 h

experiment was not permitted due to the heat resistance of
para polystyrene.
3.2.3 Effects of Liquid/Solid Ratio on Elemental Content
The content of Al and K at different liquid/solid ratios is
shown in Fig. 6, which reveals that the content of Al and K
decreases with the liquid/solid ratio when the liquid/solid
ratio is less than 10 cm3/g. A further increase in the liquid/
solid ratio leads to only a small additional increase in con-
tent. This indicates that a liquid/solid ratio of 10 cm3/g is
most favorable for leaching of Al and K impurities from
quartz sand.
3.2.4 Interactive Effects of Different Factors
The results and extreme difference analysis of the orthogonal
experiment are shown in Table 3. The optimal leaching con-
ditions are shown in Table 4. In particular, the following can
be noted:
(1) The effect of hydrochloric acid concentration (A) is most
significant.
(2) The effect of leaching time (C) is more significant.
(3) The effect of ammonia chloride concentration (D) is
significant.
(4) The effect of hydrofluoric acid concentration (B) is not
significant.

Fig. 6 Effects of liquid/solid ratio

on content of Al and K: leaching
temperature, 280 °C; NH4Cl con-
centration, 0.4 mol/dm3; HCl
concentration, 0.8 mol/dm3; HF
concentration, 0.2 mol/dm3;
leaching time, 3 h
 Mining, Metallurgy & Exploration

Table 3 Extreme difference

analysis of the results of the Test number Factors Results
orthogonal experiment
A B C D Al K Total

1 1(0.2) 1(0.0) 1(2) 1(0.4) 52.674 3.816 56.490

2 1 2(0.1) 2(3) 2(0.8) 51.432 3.743 55.175
3 1 3(0.2) 3(4) 3(1.2) 50.322 3.706 54.028
4 2(0.5) 1 2 3 48.365 3.675 52.040
5 2 2 3 1 48.142 3.056 51.198
6 2 3 1 2 49.353 3.700 53.053
7 3(0.8) 1 3 2 43.327 1.561 44.888
8 3 2 1 3 45.598 1.774 47.372
9 3 3 2 1 47.123 1.979 49.102
K1 165.693 153.418 156.915 156.790
K2 156.291 153.745 156.317 153.116
K3 141.362 156.183 150.114 153.44
k1 55.231 51.139 52.305 52.263
k2 52.097 51.248 52.106 51.039
k3 47.121 52.061 50.038 51.147
Best level 3 1 3 2
Rj 8.110 0.109 2.267 1.225
Decreasing sequence A3 C3 D2 B1

3.2.5 Effects of Leaching Time on Elemental Content
The extreme difference analysis indicates that the effect of
leaching time is more significant. Therefore, a leaching
experiment with longer leaching time was completed to
achieve the best effect (Fig. 7). The content of Al and K
was reduced from 43.33 and 1.561 μg·g−1 to 41.52 and
1.214 μg·g−1, respectively, when leaching time was in-
creased from 4 to 6 h, but their content increased with
increased leaching time from 6 to 8 h.
The optimal removal rate for muscovite is 98.97% based
on the removal rate of K when the optimal leaching conditions
in Table 5 are adopted. The chemical purification process not
only efficiently removes Al and K mainly occurring in mus-
covite, but also leaches Fe within hematite. As shown in
Table 6, the total content of the main impurity elements
in quartz concentrate is reduced from 619.0 μg·g−1 to
91.89 μg·g−1 by the combined process of calcination and
pressure leaching. The quartz concentrate can be used to
prepare high-performance aluminum boron silicate glass
that is widely applied in the thin-film-transistor liquid-
Table 4 Optimal leaching conditions
Factor HCl HF Leaching time NH4Cl
Condition 0.8 mol/dm3 0.0 mol/dm3 4 h 0.8 mol/dm3
crystal display (TFT-LCD) industry [34, 35]. With further
processing [32], the application of the quartz concentrate
can become more widespread.
4 Discussion
4.1 Effects of Oxidizing Calcination on Muscovite
Structure
Mineral muscovite can be transformed into active substances
by the process of oxidizing calcination. During this process,
the color of the muscovite changes from gray to khaki (Fig. 8a
and b) at polarized light. A possible reason is that some Fe2+
commonly occurring in muscovite is oxidized to Fe3+.
Because muscovite is a transparent mineral, the reflective
property of muscovite in quartz ore is poor (Fig. 8c). As
shown in Fig. 8d, reflected light of muscovite in calcined
quartz sand is very strong because the irregular structure of
the calcined muscovite leads to a high reflection possibility
for polarized light. This indicates that the oxidizing calci-
nation process not only damages the surface structure of
muscovite (Fig. 8b), but also promotes aberration of the
internal structure.
The calcination process commonly leads to an ordered col-
lapse of the muscovite structure. The bright-colored interfer-
ence color of muscovite disappears during crushing and grind-
ing of bulk quartz ore. As shown in Fig. 9a and b, the
Mining, Metallurgy & Exploration
Fig. 7 Effects of leaching time on
content of Al and K: L/S ratio,
10 cm3/g; leaching temperature,
280 °C; HCl concentration,
0.8 mol/dm3; NH4Cl concentra-
tion, 0.8 mol/dm3
interference color of muscovite in quartz sand is gray, al-
though there are a few color halos at crossed and reflected
light. As shown in Fig. 9(a1, a2) and (b1, b2), the calcined
muscovite shows obvious sky blue and dark yellow at
crossed-polarized light and crossed-reflected light, respective-
ly. In particular in Fig. 9(a1) and (b1), distribution of the sky
blue is inseparably linked with directional fractures in Fig. 8b,
which indicates that the ordered collapses are widely distrib-
uted around the calcined muscovite. Meanwhile, the ordered
fractures promote a refraction of transmitted and reflected
light, and allow the release of light of certain wavelengths at
specific angles.
SEM and TEM analyses show that the surface and crystal
structures of mineral muscovite in quartz sand are destroyed
during high-temperature calcination. As illustrated in Fig. 10a,
the muscovite is divided into several fragments. With further
calcination, the surface fragments are transformed into micron-
grade and nano-grade active structures (Fig. 10b). A possible
reason is that evaporation of interlayer and constitution water
leads to an increase in interlayer spacing of muscovite (Formula
1). As shown in Fig. 11, the regular atomic arrangement of
muscovite in quartz sand is disorganized after oxidizing calci-
nation at 900 °C. The calcination at 900 °C triggers the dehy-
droxylation of muscovite and further promotes a structural dis-
tortion of AlVI–O octahedrons close to the interlayer [31]. Lin
et al. showed that the active structures mainly include Si-O-Al,
Al-O-K and Si-O-K (Formula 2) [31]. The calcination process
Table 5 Optimal leaching
conditions Factor HCl
Condition 0.8 mol/dm3
provides favorable conditions for pressure leaching of trace
muscovite by transforming crystal muscovite into active struc-
tures. Moreover, the active structures may be reacted with
quartz to form other stable phases such as andalusite [36].
These stable phases in the interface of quartz and muscovite
can prevent further migration of Al and K of muscovite to
quartz particles at high temperatures.
K2 O⋅3Al2 O3 ⋅6SiO2 ⋅2H2 O→K2 O⋅3Al2 O3 ⋅6SiO2 þ 2H2 O↑ ð1Þ
K2 O⋅3Al2 O3 ⋅6SiO2 →Si−O−Al þ Al−O−K þ Si−O−K ð2Þ
4.2 Effects of Catalytic Pressure Leaching
on Muscovite
The crystal structure of mineral muscovite can also be dam-
aged by later pressure leaching, although the active structures
caused by calcination are efficiently dissolved. As shown in
Fig. 12, directional fractures in muscovite develop into com-
plicated and crossed fractures. Only bright yellows at different
light are detected. The possible reason is that only the yellow
light has a slight loss due to its longer wavelength relative to
blue light. This indicates that structure ordering of the calcined
muscovite is further disorganized by the pressure leaching.
Meanwhile, disordering of the crystal structure promotes the
dissolution of muscovite during later pressure leaching.
Leaching time NH4Cl L/S ratio Leaching temperature
6h 0.8 mol/dm3 10 cm3/g 280 °C
 Mining, Metallurgy & Exploration

Table 6 Content of main impurity elements in quartz concentrate (μg·g−1)

Element Al K Fe Mg Na B Ti Ca P Zr S Others Total

Content 41.52 1.214 1.139 4.881 11.29 8.773 4.886 4.544 5.001 6.451 – 2.192 91.89

(–) = below the limit of detection

Based on the above-described leaching experiments, the
content relationship of Al and K is shown in Fig. 13. There
are four obvious stages (a, b, c, d in Fig. 13) used to describe
the dissolution mechanisms of muscovite from quartz sand.
For the amount of harmful elements, Al (352.7 μg·g−1) and K
(118.1 μg·g−1), EDS analysis in Fig. 10 shows that muscovite
mainly contains Al (19.16 wt.%), K (8.40 wt.%), Mg
(0.31 wt.%) and Fe (0.28 wt.%). The mass ratio of Al and K
in muscovite is about 2.28.
The ΔAl/ΔK ratio for stage Ba^ is about 2.59 according to
the content of Al and K in quartz ore. The value is slightly
greater than 2.28 (Al/K ratio in Fig. 10), and is possibly
caused by a rapid release of Al and K in the active structures
transformed from mineral muscovite. Al remaining in the ac-
tive substances is finally dissolved at stage Bb^, which repre-
sents a later stage Ba^. Combining stages Ba^ and Bb^, it is
clear that K in muscovite is dissolved ahead of the lattice Al
because most of K occurs in the interlayer, whereas Al bound
in the muscovite lattice is dissolved only with further disorga-
nization of the active substances.
Obvious differences in the ΔAl/ΔK ratio between stages
Bb^ and Bc^ (30.25 and 0.55) indicate a critical change in
reaction mechanisms. Some structural distortion of crystal
muscovite, which was not destroyed during calcination,
occurs in stage Bc^. Similarly, the interlayer K is dissolved
ahead of Al bound in the muscovite structure. During stage
Bd^, Al and K are released in a certain proportion (ΔAl/ΔK
ratio = 7.64) after the structural distortion in stage Bc^. The
ΔAl/ΔK ratio of crystal muscovite dissolution is about
2.79, slightly greater than 2.59. The slight deviation in
the ΔAl/ΔK ratio could be caused by Al dissolution from
quartz or other gangue minerals. The leaching process can
be described by two formulas:
Si−O−Al þ Al−O−K þ Si−O−K þ Hþ →Si−OH
þ Al3þ þ Kþ þ H2 O ð3Þ
K2 O⋅3Al2 O3 ⋅6SiO2 þ 20Hþ →6Al3þ þ 2Kþ þ 6H2 SiO3
þ 4H2 O ð4Þ
The HCl-NH4Cl pressure leaching process can save mas-
sive HCl consumption via the catalytic performance of NH4+.
As shown in Fig. 14, the NH4Cl added in leaching solutions

Fig. 8 Polarized light images of

muscovite and calcined
muscovite in quartz sand: a
muscovite at polarized light (PL),
b calcined muscovite (PL), c
muscovite at reflected and
polarized light (RPL), d calcined
muscovite (RPL)
Mining, Metallurgy & Exploration

Fig. 9 Polarized light images of

muscovite and calcined
muscovite: a muscovite (XPL),
(a1, a2) calcined muscovite
(XPL), b muscovite (RXPL), (b1,
b2) calcined muscovite (RXPL)

can strongly promote the removal of Al, which is seen by The catalytic pressure leaching reaction is based on the
comparing curves 1 and 4 within 6 h. The contrast between hydrolytic equilibrium of NH4+ at high temperature and pres-
curves 1 and 2 indicates that the NH4Cl reduces 75% of acid sure. The hydrolysis of Al3+, as a product of formulas (3) and
consumption, at least when leaching time ranges from 4 to 6 h. (4), may be triggered by the elevated temperature (Formula 5)

Fig. 10 Secondary electron

images of muscovite in calcined
quartz sand (900 °C for 5 h) [25]
 Mining, Metallurgy & Exploration

Fig. 11 Transmission electron microscopy images of muscovite before and after calcination: a and b muscovite in quartz sand, c muscovite in calcined
quartz sand

and Si-O− structure (Formula 6) in close layers when the H+ is
consumed in large quantities [37, 38].
Al3þ þ 3H2 O⇋AlðOHÞ3 þ 3Hþ ΔH > 0
2Al3þ þ 3SiO3 2− þ 6H2 O⇋2AlðOHÞ3 þ 3H2 SiO3
The NH4+ in the leaching solution was polarized and then
hydrolyzed to provide more H+ (Formula 7). With hydrolytic
equilibrium of NH4+, hydrolysis of Al3+ was impeded, but
formulas (3) and (4) promoted. Furthermore, the NH4+ can
screen negative effects of the Si-O− structure on Al3+ diffusion
by a preferential formula (8).
NH4 þ þ H2 O⇋NH3 ⋅H2 O þ Hþ ΔH > 0
2NH4 þ þ SiO3 2− þ 2H2 O⇋2NH3 ⋅H2 O þ H2 SiO3
Furthermore, the influence of Cl− on Al3+leaching, es-
pecially for the dissolution process, also cannot be ignored
[39]. The solubility of metal chlorides including AlCl3,
ð5Þ FeCl3, CaCl2 and TiCl4 is generally higher than that of
their sulfates. Thus, the Cl− from NH4Cl can promote dis-
ð6Þ
solution of metal impurities. The increased content of Al
and K in Figs. 4 and 7 may be caused by sorption of
H2SiO3 on Al3+ and K+ [25, 30].
In contrast to the traditional HCl-HF leaching system
[6], the HCl-NH4Cl system shows obvious advantages in
purification efficiency and capacity during quartz process-
ing. At the same leaching time (6 h), more elemental im-
purities in quartz sand can be removed by increasing the
temperature and pressure of the leaching reaction. More
ð7Þ
importantly, HCl consumption can be extensively reduced
ð8Þ from several mol/dm3 to 0.8 mol/dm3 simply by adding

Fig. 12 Polarized light images of

leached muscovite: a leached
muscovite (PL), b leached
muscovite (XPL), c leached
muscovite (RPL), d leached
muscovite (RXPL); L/S ratio,
10 cm3/g; leaching temperature,
280 °C; HCl concentration,
0.2 mol/dm3; NH4Cl concentra-
tion, 0.2 mol/dm3; leaching time,
4h
Mining, Metallurgy & Exploration
Fig. 13 The content relationship of Al and K
0.8 mol/dm3 of NH4Cl. Indeed, the purification efficiency
and capacity of the leaching agents is not reduced, but
rather is increased, when no fluorides are used. In addition,
possible environmental pollution from fluorine is avoided.
Similar to muscovite, the hematite mainly containing trace
element Fe can also be efficiently removed by the fluoride-
free processing technique.
Gangue minerals including muscovite and hematite can be
effectively separated from the hydrothermal quartz by the
combined process of oxidizing calcination and catalytic pres-
sure leaching. The oxidizing calcination process not only de-
stroys crystal structures of the gangue minerals, but also
removes fluid inclusions (important sources of Na and Ca)
in quartz [40]. Meanwhile, exposure probabilities of the min-
eral impurities are enhanced during the calcination process. In
general, the oxidizing calcination process has a positive influ-
ence on the removal of impurity elements through catalytic
pressure leaching.
Fig. 14 Effects of leaching time on content of elemental Al: L/S ratio,
10 cm3/g; leaching temperature, 280 °C
Fig. 15 Particle sizes and specific areas of quartz sand at different
conditions: quartz sand (QS), calcined quartz sand (CQS), quartz
concentrate (QC)
4.3 Effects of Separation Process on Quartz Particles
Unlike fluoric leaching, HCl-NH4Cl pressure leaching can
selectively dissolve gangue minerals in the surface/
interface of quartz grains. As shown in Fig. 15, there is
only a 1.54% reduction in particle size relative to quartz
ore when 86.89% of quartz sand concentrate is larger than
100 μm. Meanwhile, the specific area of quartz sand in-
creases from 14.99 m2/kg to 16.59 m2/kg. This tiny in-
crease of 10.67% indicates that this process without HF
shows limited influence on the particle size of quartz sand.
Hence, the chemical processing techniques show high se-
lectivity in purifying quartz sand by transforming mineral
muscovite into active structures during oxidizing calcina-
tion, and then dissolving the active substances during cat-
alytic pressure leaching.
5 Conclusions
(1) The content of Al and K was reduced to 41.52 μg·g−1
and 1.214 μg·g−1, respectively, when the calcined
quartz sand (900 °C for 5 h) was leached for 6 h at
280 °C by HCl-NH 4 Cl solutions. An optimal
leaching effect was obtained with 0.8 mol/dm 3 of
HCl, 0.8 mol/dm3 of NH4Cl, and a liquid/solid ratio
of 10 cm3/g. At optimal conditions, 98.97% or more
of the muscovite within the surface/interface of
quartz grains was selectively removed by the chemi-
cal processing techniques.
(2) Gangue mineral muscovite within the surface/
interface of quartz grains from a hydrothermal depos-
it was activated during oxidizing calcination and then
effectively separated by catalytic pressure leaching.

Ammonia chloride was hydrolyzed to provide a sta-
ble leaching environment and to inhibit the hydroly-
sis of Al3+ caused by triggering of elevated tempera-
ture and Si-O− structure.
Acknowledgements Financial support for the project was provided by
the National Natural Science Foundation of China (51604205,
51774223).
Compliance with ethical standards
Conflict of Interest The authors declare no conflict of interest.
References
1. Scott HS (1957) The decrepitation method applied to minerals with
fluid inclusions. Econ Geol 43:637–654. https://doi.org/10.2113/
gsecongeo.43.8.637
2. Smith FG (1957) Decrepitation characteristics of igneous rocks.
Can Mineral 6:78–86
3. Wang L, Li CX, Wang Y, Yin DQ (2011) China technologies pres-
ent of high-purity quartz processing and the development proposi-
tions. J Mineral Petrol 31:110–114. https://doi.org/10.3969/j.issn.
1001-6872.2011.04.017
4. Vatalis KI, Charalampides G, Platias S, Benetis NP (2014) Market
developments and industrial innovative applications of high purity
quartz refines ☆. Proc Econ Fin 14:624–633. https://doi.org/10.
1016/S2212-5671(14)00751-5
5. Wang L, Dang CP, Li CX, Wang Y, Wei YY, Xia JZ, Pan JL (2014)
Technology of high-purity quartz in China: status quo and prospect.
Earth Sci Front 21:267–273. https://doi.org/10.13745/j.esf.2014.
05.021
6. Santos MFM, Fujiwara E, Schenkel EA, Enzweiler J, Suzuki CK
(2015) Processing of quartz lumps rejected by silicon industry to
obtain a raw material for silica glass. Int J Miner Process 135:65–
70. https://doi.org/10.1016/j.minpro.2015.02.002
7. Fraundorf GK, Shive L (1990) Transmission electron microscope
study of quartz crucibles used in growth of Czochralski silicon. J
Cryst Growth 102:157–166. https://doi.org/10.1016/0022-
0248(90)90897-T
8. Minami T, Maeda S, Higasa M, Kashima K (2011) In-situ observa-
tion of bubble formation at silicon melt–silica glass interface. J
Cryst Growth 318:196–199. https://doi.org/10.1016/j.jcrysgro.
2010.10.075
9. Yamahara K, Huang X, Sakai S, Utsunomiya A, Tsurita Y,
Hoshikawa K (2001) Surface of silica glass reacting with silicon
melt: effect of raw materials for silica crucibles. Jpn J Appl Phys 40:
1178–1182. https://doi.org/10.1143/JJAP.40.1178
10. Edvardmikhailovich B, Nick C, Igorantonovich K,
Mamikonaramovich M, John S, Ivanmerabovich T (2008)
Killing bacteria present on surfaces in films or in droplets using
microwave UV lamps. World J Microbiol Biotechnol 24:761–769.
https://doi.org/10.1007/s11274-007-9536-y
11. Macaluso AL, Mitchell DL, Sanders RW (2009) Direct effects of
UV-B radiation on the freshwater heterotrophic nanoflagellate
Paraphysomonas sp. Appl Environ Microbiol 75:4525–4530.
https://doi.org/10.1128/AEM.02803-08
12. Dhamrin M, Saitoh T, Kamisako K, Yamada K, Araki N, Yamaga I,
Sugimotoc H, Tajimac M (2009) Technology development of high-
quality n-type multicrystalline silicon for next-generation ultra-thin
crystalline silicon solar cells. Sol Energy Mater Sol Cells 93:1139–
1142. https://doi.org/10.1016/j.solmat.2009.02.011
Mining, Metallurgy & Exploration
13. Kvande R, Arnberg L, Martin C (2009) Influence of crucible and
coating quality on the properties of multicrystalline silicon for solar
cells. J Cryst Growth 311:765–768. https://doi.org/10.1016/j.
jcrysgro.2008.09.152
14. Griscom DL (2006) Self-trapped holes in pure-silica glass: a history
of their discovery and characterization and an example of their
critical significance to industry. J Non-Cryst Solids 352:2601–
2617. https://doi.org/10.1016/j.jnoncrysol.2006.03.033
15. Schreiber A, Kühn B, Arnold E, Schilling FJ, Witzke HD (2005)
Radiation resistance of quartz glass for VUV discharge lamps. J
Phys D Appl Phys 38:3242–3250. https://doi.org/10.1088/0022-
3727/38/17/S28
16. Kuzuu N, Horikoshi H, Nishimura T, Kokubo Y (2003) Effects of
heat treatment on absorption bands in OH-free and OH-containing
fused quartz. J Appl Phys 93:9062–9071. https://doi.org/10.1063/1.
1572542
17. Nie YM, Lu XL, Niu FS (2013) Purification experiment research of
quartz sand. Appl Mech Mater 389:346–348. https://doi.org/10.
4028/www.scientific.net/AMM.389.346
18. Veglió F, Passariello B, Barbaro M, Plescia P, Marabini AM (1998)
Drum leaching tests in iron removal from quartz using oxalic and
sulphuric acids. Int J Miner Process 54:183–200. https://doi.org/10.
1016/S0301-7516(98)00014-3
19. Wang L, Sun W, Hu YH, Xu LH (2014) Adsorption mechanism of
mixed anionic/cationic collectors in muscovite–quartz flotation sys-
tem. Miner Eng 64:44–50. https://doi.org/10.1016/j.mineng.2014.
03.021
20. Li X, Li T, Gao J, Huang H, Li L, Li J (2016) A novel Bgreen^
solvent to deeply purify quartz sand with high yields: a case study. J
Ind Eng Chem 35:383–387. https://doi.org/10.1016/j.jiec.2016.01.
018
21. Sarit D, Oliver S, Halls MD, Sungho C, Chabal YJ, Feldman LC
(2009) Chemical properties of oxidized silicon carbide surfaces
upon etching in hydrofluoric acid. J Am Chem Soc 131:16808–
16813. https://doi.org/10.1021/ja9053465
22. Larsen E, Kleiv RA (2016) Flotation of quartz from quartz-feldspar
mixtures by the HF method. Miner Eng 98:49–51. https://doi.org/
10.1016/j.mineng.2016.07.021
23. An J, Lee HA, Lee J, Yoon HO (2015) Fluorine distribution in soil
in the vicinity of an accidental spillage of hydrofluoric acid in
Korea. Chemosphere 119C:577–582. https://doi.org/10.1016/j.
chemosphere.2014.07.043
24. Kline WE, Fogler HS (1981) Dissolution kinetics: the nature of the
particle attack of layered silicates in HF. Chem Eng Sci 36:871–
884. https://doi.org/10.1016/0009-2509(81)85041-5
25. Lin M, Pei ZY, Lei SM, Liu YY, Xia ZJ, Xie FX (2018) Trace
muscovite dissolution separation from vein quartz by elevated tem-
perature and pressure acid leaching using sulphuric acid and am-
monia chloride solutions. Physicochem Probl Miner Process 54:
448–458. https://doi.org/10.5277/ppmp1839
26. Lin M, Liu YY, Lei SM, Ye Z, Pei ZY, Li B (2018) High-efficiency
extraction of Al from coal-series kaolinite and its kinetics by calci-
nation and pressure acid leaching. Appl Clay Sci 161:215–224.
https://doi.org/10.1016/j.clay.2018.04.031
27. Xiong K, Lei SM, Zhong LL, Pei ZY, Yang YY, Zang YY (2016)
Thermodynamic mechanismand purification of hot press leaching
with vein quartz. China Min Mag 25:129–132. https://doi.org/10.
3969/j.issn.1004-4051.2016.02.025
28. Lin M, Lei SM, Pei ZY, Liu YY, Xia ZJ, Xie FX (2018) Application
of hydrometallurgy techniques in quartz processing and purifica-
tion: a review. Metall Res Technol 115:303. https://doi.org/10.1051/
metal/2017105
29. Xue NN, Zhang YM, Liu T, Huang J, Zheng QS (2017) Effects of
hydration and hardening of calcium sulfate on muscovite dissolu-
tion during pressure acid leaching of black shale. J Clean Prod 149:
989–998. https://doi.org/10.1016/j.jclepro.2017.02.152
Mining, Metallurgy & Exploration
30. Lin M, Pei ZY, Lei SM (2017) Mineralogy and processing of hy-
drothermal vein quartz from Hengche, Hubei Province (China).
Minerals 7:161. https://doi.org/10.3390/min7090161
31. Pei ZY, Lin M, Liu YY, Lei SM (2018) Dissolution behaviors of
trace muscovite during pressure leaching of hydrothermal vein
quartz using H2SO4 and NH4Cl as leaching agents. Minerals 8:
282. https://doi.org/10.3390/min8020060
32. Lin M, Pei ZY, Li YB, Liu YY, Wei ZL, Lei SM (2018) Separation
mechanism of lattice-bound trace elements from quartz by KCl-
doping calcination and pressure leaching. Miner Eng 125:42–49.
https://doi.org/10.1016/j.mineng.2018.05.029
33. Götze J, Plotze M, Graupner T, Hallbauer DK, Bray CJ (2004)
Trace element incorporation into quartz: a combined study by
ICP-MS, electron spin resonance, cathodoluminescence, capillary
ion analysis, and gas chromatography 1. Geochim Cosmochim
Acta 68:3741–3759. https://doi.org/10.1016/j.gca.2004.01.003
34. Ellison A, Cornejo IA (2010) Glass substrates for liquid crystal
displays. Int J Appl Glas Sci 1:87–103. https://doi.org/10.1111/j.
2041-1294.2010.00009.x
35. Gao X, Zhang Q, Yu J, Tang W, Li Y, Lu A (2018) Effect of
replacement of Al2O3 by Y2O3 on the structure and properties of
alkali-free boro-aluminosilicate glass. J Non-Cryst Solids 481:98–
102. https://doi.org/10.1016/j.jnoncrysol.2017.10.032
36. Liu C, Lin J (2008) Influence of calcination temperature on dielec-
tric constant and structure of the micro-crystalline muscovite. China
Non-Met Min Ind Her 5:38–46. https://doi.org/10.3969/j.issn.
1007-9386.2008.05.012
37. Bogatko S, Moens J, Geerlings P (2010) Cooperativity in Al3+
hydrolysis reactions from density functional theory calculations. J
Phys Chem A 114:7791–7799. https://doi.org/10.1021/jp102787e
38. Hou XX, Dong SN, Zhang J, Shu-Ping BI (2016) DFT study of the
static structural and ~(27)Al−/~(17)O−/~1H-NMR characteristics
for the third hydration shell of Al~(3+)(aq) complexes. J Anal Sci
32:149–155. https://doi.org/10.13526/j.issn.1006-6144.2016.02.
001
39. Lee KY, Yoon YY, Jeong SB, Chae YB, Ko KS (2009) Acid
leaching purification and neutron activation analysis of high purity
silicas. J Radioanal Nucl Chem 282:629–633. https://doi.org/10.
1007/s10967-009-0318-x
40. Lin M, Pei ZY, Liu YY, Xia ZJ, Xiong K, Lei SM, Wang EW
(2017) High-efficiency trace Na extraction from crystal quartz ore
used for fused silica — a pretreatment technology. Int J Miner
Metall Mater 24:1075–1086. https://doi.org/10.1007/s12613-017-
1498-y