minerals

Article
The Role of Water Glass in the Flotation Separation
of Fine Fluorite from Fine Quartz
Guofan Zhang, Yawen Gao, Wei Chen * and Dezhi Liu
School of Mineral Processing and Bioengineering, Central South University, Changsha 410083, China;
zhangguofan2002@163.com (G.Z.); gaoyawencsu@163.com (Y.G.); liudezhi@csu.edu.cn (D.L.)
* Correspondence: csuchenwei@csu.edu.cn; Tel: +86-0731-8883-0913

Received: 8 August 2017; Accepted: 23 August 2017; Published: 28 August 2017

Abstract: Fluorite is the principal mineral of fluorine and usually coexists with quartz in deposits.
The removal of fine quartz in fluorite concentrate is the main problem in fluorite flotation. In this
study, the flotation tests on fluorite, quartz and a weight equivalent mixture (all less than 10 µm)
using water glass (with different modulus) as depressants and sodium oleate as collector were
conducted. The mechanism of fine quartz entering the fluorite concentrate was investigated through
optional observations and rheology measurements on the flotation pulp. The particle interactions
between fine fluorite and quartz under flotation-related conditions were analyzed through zeta
potential measurements and DLVO calculations. The results revealed that there existed strong
hetero-coagulation between fluorite and quartz particles in the flotation pulp, which could be the
main reason for the quartz entering the fluorite concentrate in the flotation process. Water glass with
higher modulus could eliminate the hetero-coagulation more totally but inevitably influences the
flotability of fluorite.

Keywords: flotation; water glass modulus; hetero-coagulation; fluorite; quartz

1. Introduction
Fluorite is the principal mineral of fluorine and is mainly used for the production of hydrofluoric
acid and as a flux in steel making. Fluorite usually coexists with calcite, quartz and other silicate
minerals in deposits. By now, fluorite is mostly recovered from these gangue minerals by froth flotation,
through which can produce fluorite concentrate with grade up to 99% (by weight). In fluorite flotation,
fatty acids and their derivatives are used as collectors for fluorite [1,2]. The common opinion for the
collecting mechanism is the chemisorption that derives from the chemical interactions between the
exposed Ca2+ on fluorite surface and carboxyl (–COO–) in the collectors [3,4].
The major requirement for the flotation process is the removal of the large amount of quartz in
the flotation feeds. For this purpose, depressants are often added to depress the flotation of quartz.
Common depressants used in fluorite flotation are water glass, phosphate and some kind of colloid
such as tannin and starch [5–7]. Of all published depressants, water glass is the most widely used one
for its low cost and stable depressant effect.
Water glass is a soluble silicate (K2 O·nSiO2 or Na2 O·nSiO2 ) that is manufactured by the reaction
of alkali metal oxides (K2 O or Na2 O) and silicon dioxide (SiO2 ) [8]. It is widely used in the mineral
processing industries as dispersant or modifier. The molar ratio (n) of silicon dioxide to alkali metal
oxides, termed modulus, is an important parameter for water glass used in flotation plants [9].
The modulus has a direct effect on the properties of the water glass, such as solubility, viscosity,
dispersion and depressant ability. It has been reported that when the modulus increases, the depression
effect of water glass on silicate minerals will increase; however, the solubility of the water glass will
decrease and in turn limits its utilization [8,10]. Water glass has long been the depressant for quartz

Minerals 2017, 7, 157; doi:10.3390/min7090157 www.mdpi.com/journal/minerals

Minerals 2017, 7, 157 2 of 14
Minerals 2017, 7, 157 2 of 14

for quartz and other silicate minerals in the flotation of oxide ores [11], salt-type ores [12] and
sulphide
and otherores [13],minerals
silicate especially for the
in the flotation
flotation of fluorite
of oxide [7]. salt-type ores [12] and sulphide ores [13],
ores [11],
However,
especially for thetheflotation
flotationofseparation
fluorite [7].of fluorite from quartz using water glass is not so effective, as
thereHowever,
is always athe small amount
flotation of fine quartz
separation (less than
of fluorite from10quartz
μm) inusing
the fluorite
water concentrate.
glass is not so The floated
effective,
fine quartz
as there in fluorite
is always a smallconcentrate
amount of has fine been
quartz reported to10
(less than beµm)
the in
result of metal
the fluorite ion activation
concentrate. on the
The floated
fine quartz that defeats
in fluorite the depressant
concentrate effectreported
has been of the water
to be glass [13–15].
the result It hasion
of metal been demonstrated
activation on the that
fine
the entrained
quartz fine quartz
that defeats is the frotheffect
the depressant entrainment,
of the water which may
glass also beItan
[13–15]. hasimportant factor that entrains
been demonstrated that the
the fine quartz
entrained into the
fine quartz is fluorite
the frothconcentrate
entrainment, [16–18].
whichTo date,
may little
also be work has beenfactor
an important conducted on the
that entrains
effect of the modulus of water glass on the flotation of fluorite and the existence
the fine quartz into the fluorite concentrate [16–18]. To date, little work has been conducted on of fine quartz in the
fluorite
effect ofconcentrate.
the modulus of water glass on the flotation of fluorite and the existence of fine quartz in the
In this
fluorite study, the effect of water glass modulus (n) on the separation of fine fluorite and quartz
concentrate.
was studied. The flotation
In this study, the effect tests on theglass
of water single minerals(n)
modulus ofonfine fluorite
the and quartz
separation of fine(all less than
fluorite and 10 μm)
quartz
as
waswell as mixed
studied. The minerals
flotation were
tests onconducted
the singleusing waterofglass
minerals (WG) (with
fine fluorite modulus
and quartz (allranging
less than from
10 µm)1.0
to
as 3.5)
wellas asdepressant
mixed minerals and sodium oleate (NaOl)
were conducted usingaswater
collector.
glass The
(WG) effect ofmodulus
(with water glass modulus
ranging fromon 1.0the
to
level
3.5) asof aggregation
depressant betweenoleate
and sodium fine (NaOl)
fluoriteas and quartz
collector. Thewaseffectdiscussed withmodulus
of water glass the zetaonpotential
the level
measurements,
of aggregation between optical observation
fine fluorite and rheology
quartz was measurements.
discussed withThe the particle interactions
zeta potential between
measurements,
the fineobservation
optical fluorite andand quartz withmeasurements.
rheology treatment of different modulus
The particle were compared
interactions between the byfine
the fluorite
DLVO
calculations,
and quartz with on which
treatmentbasisofthe mechanism
different modulus of the fine
were quartz entering
compared the fluorite
by the DLVO concentrate
calculations, was
on which
proposed.
basis the mechanism of the fine quartz entering the fluorite concentrate was proposed.

Materials and Methods

2. Materials

2.1. Materials
2.1. Materials and
and Regents
Regents
The samples
The samplesofoffluorite
fluoriteand and quartz
quartz were
were all acquired
all acquired from from Chenzhou,
Chenzhou, Hunan,Hunan, China.
China. Hand-
Hand-selected crystals of the two minerals were crushed to − 1 mm in a laboratory
selected crystals of the two minerals were crushed to −1 mm in a laboratory roll crusher and then roll crusher
and theninground
ground in a planetary
a planetary mill−10
mill to get μm−
to get 10 µm samples.
samples. A pure
A part of part of pure sample
sample was further
was further ground ground
to −2
to − 2 µm in agate mortar for Zeta potential measurements. Quantitative X-ray
μm in agate mortar for Zeta potential measurements. Quantitative X-ray diffraction (XRD) analysis diffraction (XRD)
analysis1)
(Figure (Figure
of the 1) of the samples
samples confirmed confirmed
purity of purity
99.56ofwt99.56 wtfluorite
% for % for fluorite andwt
and 97.46 97.46
% forwt quartz.
% for quartz.
The particle
The particle cumulative
cumulativesize sizedistributions
distributionsofofthetheabove
abovematerial
materialsamples
sampleswereweremeasured
measured with
with a
a Malvern Mastersizer 2000 (Malvern Instruments Ltd, Worcestershire, UK),
Malvern Mastersizer 2000 (Malvern Instruments Ltd, Worcestershire, UK), by light scattering. The by light scattering.
The measurement
measurement was was performed
performed usingusing a very
a very dilute
dilute suspension
suspension (about(about
0.1 wt0.1
%wt % solids)
solids) conditioned
conditioned with
dispersants followed by 20 s of ultrasonic dispersion. The results are shown in Figure 2. The D50Dof
with dispersants followed by 20 s of ultrasonic dispersion. The results are shown in Figure 2. The 50
of the fluorite and quartz samples was all
the fluorite and quartz samples was all about 5 μm. about 5 µm.

(a)

Figure 1. Cont.
Minerals 2017, 7, 157 3 of 14
Minerals 2017, 7, 157 3 of 14

Minerals 2017, 7, 157 3 of 14

(b)
(b)
Figure 1. X-ray diffraction (XRD) spectrums of single fluorite (a) and quartz (b).
Figure 1. X-ray
Figure diffraction
1. X-ray diffraction(XRD)
(XRD) spectrums ofsingle
spectrums of singlefluorite
fluorite
(a)(a)
andand quartz
quartz (b). (b).

Figure 2. Particle cumulative size distributions of the fluorite and quartz samples.
Figure 2. Particle cumulative size distributions of the fluorite and quartz samples.
Figure 2. Particle cumulative size distributions of the fluorite and quartz samples.
Sodium oleate (C18H33O2Na) was used as collector for fluorite and was purchased from Tianjing
Kermil
SodiumChemical
Sodium oleate (CReagents
H3333OO2Na)
18H
18
Development
2 Na)was
wasused Centre,
usedas Tianjin,
ascollector
collector China.
forfluorite
for Sodium
fluorite andwas
and hydroxide
was purchased
purchased (NaOH)
fromwas
from Tianjing
Tianjing
used as pH regulator. All of the reagents were analytical pure. Water glass with different modulus
Kermil Chemical Reagents Development Centre, Tianjin, China. Sodium hydroxide (NaOH) used
Kermil Chemical Reagents Development Centre, Tianjin, China. Sodium hydroxide (NaOH) was was
was purchased from Changsha, China. The properties are listed in Table 1. Distilled water was used
as pHasregulator.
used pH regulator.All ofAll
theofreagents werewere
the reagents analytical pure.pure.
analytical Water glassglass
Water withwith
different modulus
different was
modulus
for all tests.
purchased
was fromfrom
purchased Changsha, China.
Changsha, TheThe
China. properties are listed
properties in Table
are listed 1. Distilled
in Table water
1. Distilled waswas
water used for
used
all tests.
for all tests. Table 1. Chemical composition and properties of water glass.

Modulus SiOTable
2 Na 2O
1. ChemicalSolids (wt %) and H
composition 2O (wt %)
properties Viscosity (mPa·s)
of water glass.
Table 1. Chemical composition and properties of water glass.
1.0 23.8 23.8 47.6 52.4 2.06
Modulus 1.5
Modulus SiO23.04
2 Na215.36
SiO 2O NaSolids
2O 38.4
(wt %)(wt %)H2O
Solids 61.6
(wt
H 2 O%)
(wt %) 4.62 (mPa
Viscosity
Viscosity ·s)
(mPa·s)
1.0 2.0 1.0 23.821.6 10.8
23.8
23.8 32.4
23.8 47.6 47.6 67.6
52.4 52.4 21.46 2.06
2.06
1.5 2.5 1.5 23.0428.9323.04 11.57 15.36 38.4
15.36 40.5 38.4 59.5
61.6 61.6 127.57
4.62
4.62
3.0 2.0 20.6721.6 6.92 10.8 27.68 72.32 67.6 10.15
2.0 21.6 10.8 32.4 32.4 67.6 21.46
21.46
3.5 2.5 27.928.93 8.1 11.57 34.6 40.5 65.4 59.5 75.16
127.57
2.5 3.0
28.93 20.6711.57 6.92
40.5 27.68 59.572.32 127.57
10.15
3.0 20.67
3.5 Tests
2.2. Flotation 6.92
27.9 8.1 27.68 34.6 72.32 65.4 10.15
75.16
3.5 27.9 8.1 34.6 65.4 75.16
Micro-flotation tests were conducted on a XFGC type mechanical agitation flotation machine
2.2. Flotation Tests machinery factory, Changchun, China) with a 40 mL cell at 1800 rpm. For single
(Jilin exploration
2.2. Flotation Tests
mineral flotation test, mineral pulp was prepared by adding 2 g mineral samples to the cell with
Micro-flotation tests were conducted on a XFGC type mechanical agitation flotation machine
Micro-flotation tests were
(Jilin exploration machinery conducted
factory, on a XFGC
Changchun, type
China) mechanical
with agitation
a 40 mL cell flotation
at 1800 rpm. Formachine
single
(Jilin exploration machinery factory, Changchun, China) with a 40 mL cell at 1800 rpm. For single
mineral flotation test, mineral pulp was prepared by adding 2 g mineral samples to the cell with
Minerals 2017, 7, 157 4 of 14

mineral flotation test, mineral pulp was prepared by adding 2 g mineral samples to the cell with
distilled water. pH was adjusted by HCl or NaOH solutions in 3 min. Depressant (if needed) and
collector were added at a designed concentration. Conditioning time for each reagent was 3 min
and flotation time was 4 min for each test. After flotation, the concentrate and tailing were collected,
filtered, dried, weighed and the recovery was determined based on solid weight distributions between
the two products. For artificial mixed minerals, mass ratio of fluorite and quartz was 1:1 for binary
mixture (1 g fluorite + 1 g quartz). The concentrate and tailing were assayed for Ca and Si. Fluorite
recovery was calculated based on CaF2 distributions between these products.

2.3. Observations of Mineral Pulp

The observation of mineral suspensions was conducted using a transmission light microscope
(OLYMPUS-CX31RTSF, Olympus corporation, Tokyo, Japan). 1 mL of suspension was sampled by a
syringe and diluted 10 times in a beaker by distilled water. Then, dilute solution was dropped on a
microslide and was flatted by a coverslip on the objective table. Around 1000 µm × 1000 µm region of
slurry can be videoed by a digital camera, so the slurry images at any recorded time can be analyzed.

2.4. Shear Yield Stress Measurements

Shear yield stress is a measure of the resistance of the pulp to the permanent deformation in shear,
or the minimum stress needed for the occurrence of flow. The yield stress of the flotation pulp is an
indicative parameter of the particle interactions between different minerals. It has been proven to be
the level of aggregation or dispersion in the mineral pulp [19,20].
The yield stress measurement was conducted with an Anton Paar MCR102 rheometer and a vane
impeller probe. The sample holder is 38 cm3 and its diameter is 27 mm. The impeller has 6 outer
blades which diameter reaches 24 mm. Each rheology measurement required a mineral pulp of 30 mL
which was prepared through the conditioning operations in the flotation cell as stated in Section 2.2.
The rheometer automatically set the distance between the base of the cup and the tip of the impeller
which was 0 mm in this study. The shear stress range for the stress sweep was between 0.01 Pa and
20 Pa and it took around 9 min to cover the stress range. The measurement procedures involved the
following steps: (1) pre-shearing of the slurry for 60 s at 300 s−1 ; (2) stabilization of the slurry for 15 s at
0 s−1 ; (3) measurement of shear strain with increasing shear stress. The yield stress was obtained from
the shear stress vs. shear strain curves where the shear strain suddenly increased under increasing
shear stress. It was calculated by the point where the tangent lines of the strain curves intersected.

2.5. Zeta Potential Measurements

Zeta potential measurements were conducted at pH 9.0 and 25 ◦ C on a Coulter Delsa440sx Zeta
analyzer instrument using 1 × 10−2 mol/L KCl as background electrolyte solution. Then, 0.03 g pure
mineral sample (−2 µm) was dispersed in 40 mL electrolyte solution using a magnetic stirrer with HCl
and NaOH adjusting pH. Flotation reagent was added at a desired concentration and conditioned for
10 min. After a standing of 5 min, the supernatant liquid was sucked out for measurement. At least
three measurements were made for a certain experimental condition. The average value and the
standard deviation were calculated.

2.6. Particle Interaction Calculations—Derjguin-Landau-Verwey-Overbeek (DLVO) Theory

According to the DLVO theory, the form and existence of particles depends on the combined
action of Van-der-Waals force and electrostatic forces. Changes in the surface potential of particles can
influence the electrostatic energy and further alter the aggregating state of mineral. On the basis of
DLVO, the total interaction energy of particles in the liquid consisted of heterogeneous minerals can be
calculated as
VTD = VW + VE (1)
Minerals 2017, 7, 157 5 of 14
Minerals 2017, 7, 157 5 of 14
where VW is Van-der-Waals energy, J. VE means electrostatic energy, J. means the total interaction
energy, J. And VW is calculated as
where VW is Van-der-Waals energy, J. VE means electrostatic energy, J. VTD means the total interaction
energy, J. And VW is calculated as V = (2)
6 AR1+ R2
VW = − (2)
where 6H ( R1 + R2 )
where
=p p p p (3)
A = ( A11 − A33 )( A22 − A33 ) (3)
where A means the Hammaker constant in vacuum. H is the separation distance. For two different
where A means the Hammaker constant in vacuum. H is the separation distance. For two different
types of particles with radius R1 and R2, VE can be calculated as
types of particles with radius R1 and R2 , VE can be calculated as
2
= + + (4)
πε a+R1 R2 2ψ01 +ψ02 p + q]
VE = (ψ01 2 + ψ02 2 )[ (4)
R1 + R2 ψ01 2 + ψ02 2
where
where 1+
p = ln 1 + e−κH (5)
p = ln( 1 −κH ) (5)
1−e
and
and
−2κH
qq==ln
ln(11− e ) (6)
(6)
where κκ is
where is the
the thickness
thickness of of the
the electric
electricdouble-layer,
double-layer,κκ==0.104 0.104nm nm−−11;; εεaa isisthe
therelative
relative dielectric
dielectric constant
of the continuous phase. εε00 and and εεrr are
are the
the permittivity
permittivity of of free
free space
space and and the
the relative
relative permittivity,
permittivity,
respectively (εaa == εε00××εrε=r 6.95
= 6.95 × −10
× 10 10C −10
−2J−1
Cm −2−1J);
−1ψm −1 ); ψ particle
0 means means surface
particle potential
surface [21].
potential [21].
0

3. Results and
3. Results and Discussion
Discussion

3.1. Single Mineral

3.1. Single Mineral Flotation
Flotation Results
Results
The effect of
The effect of pulp
pulp pH
pHandandNaOl
NaOldosage
dosageon onthe
theflotation
flotationbehaviors
behaviors ofof fine
fine fluorite
fluorite and
and quartz
quartz in
in
the presence of NaOl alone was explored and the results are shown in Figure 3. The recovery of
the presence of NaOl alone was explored and the results are shown in Figure 3. The recovery of
fluorite increased quickly with the dosage of NaOl but that of quartz seldom increased,
fluorite increased quickly with the dosage of NaOl but that of quartz seldom increased, as shown in as shown
in Figure
Figure 3a.3a.
WhenWhenNaOlNaOl dosage
dosage reached
reached 5×
5 × 10 10−5 mol/L,
−5 mol/L, the recoveries
the recoveries of fluorite
of fluorite and was
and quartz quartz was
86.56%
86.56% and 4.32%, respectively. The good collecting ability of NaOl towards fluorite
and 4.32%, respectively. The good collecting ability of NaOl towards fluorite derived from the derived from the
chemisorption
chemisorption as as stated
stated in Section 1.
in Section 1. The
The collecting
collecting ability,
ability, or
or the
the chemisorption,
chemisorption, has has aa large
large difference
difference
compared
compared fluorite with quartz in tested pH range 7–12 as in Figure 3b. The results indicated that,that,
fluorite with quartz in tested pH range 7–12 as in Figure 3b. The results indicated for
for single mineral pulp, using NaOl alone can achieve the separation of fluorite
single mineral pulp, using NaOl alone can achieve the separation of fluorite from quartz. from quartz.

(a)

Figure 3. Cont.
 Minerals 2017, 7, 157 6 of 14

Minerals 2017, 7, 157 6 of 14

Minerals 2017, 7, 157 6 of 14

(b)
(b)
Figure
Figure3.3.NaOl
NaOldosage
dosage(a)(a)and
andeffect
effectofofpH
pH(b)
(b)ononthe
theflotation
flotationperformance
performanceofoffluorite
fluoriteand
andquartz
quartzinin
Figure 3. NaOl dosage (a) and effect of pH (b) on the flotation performance of fluorite and quartz in
the absence of water glass (WG).
the absence of water glass (WG).
the absence of water glass (WG).
Figure 4 shows the flotation behaviors of fine fluorite and quartz in the presence of WG and
Figure 4 shows the
theflotation behaviors of of fine fluorite andand
quartz in the presence of WG and
WGNaOl.
NaOl.Figure
It can be shows
seen from flotation
Figure 4a behaviors
that as WG (nfine fluorite
= 2.5) dosage quartz
increased, in
thethe presence
quartz kept of and
unflotable
It can be
NaOl. It seenbefrom
can seenFigure
from 4a that4a
Figure as that
WG as (n WG
= 2.5)(ndosage
= 2.5) increased,
dosage the quartz
increased, the kept
quartz unflotable
kept and the
unflotable
and the flotation of fluorite was gradually depressed. The severe depression of fluorite was observed
flotation
and the of fluorite was gradually depressed. The severe depression of fluorite was observed when
when WGflotation
dosage of fluorite
exceeded was
15 gradually
mg/L. Figuredepressed.
4b shows the Theflotability
severe depression
of fluoriteofinfluorite was observed
the presence of WG
WG dosage
when WG dosageexceeded 15 mg/L.
exceeded Figure 4b shows the flotability of fluorite in the presence of WG of with
with different modulus with15different
mg/L. Figure
pH. It4bwasshows firstthe flotability
noted that theof fluorite
additioninof theWG
presence
exhibited WGa
different modulus with different pH. It pH.
was Itfirst noted that thethat
addition of WG exhibited a negative
negative effect on fluorite flotation. As the WG modulus increased, the fluorite flotation wasa
with different modulus with different was first noted the addition of WG exhibited
effect on fluorite
negative flotation.
effect severely
on fluorite As the WG As
flotation. modulus
the WG increased,
modulus the fluorite flotation was depressed more
depressed more in the whole pH range. When the WG increased,
modulus was theinfluorite
the range flotation was
of 1.0–2.5,
severely inmore
depressed the whole
severelypHinrange. WhenpH the WG modulus thewas in the range of 1.0–2.5, the flotation of
the flotation of fluorite wasthe whole
similar with range. Whenwith
the results WG
no modulus
WG addition.was inWhen
the range of 1.0–2.5,
the modulus
fluorite
the was similar
flotation of withwas
fluorite the results
similar with
with no WG
the addition.
results with When
no WGtheaddition.
modulus When increasedthe to 3.0–3.5,
modulus
increased to 3.0–3.5, the fluorite flotation was significantly affected. The results demonstrated that
the fluorite
increased toflotation wasfluorite
3.0–3.5,modulus
the significantly affected.
flotation The results affected.
wasfluorite
significantly demonstrated that the
The results WG with higher
demonstrated that
the WG with higher are not good for flotation.
modulus
the WG with are higher
not good for fluorite
modulus flotation.
are not good for fluorite flotation.

(a)
(a)

Figure 4. Cont.
 Minerals 2017, 7, 157 7 of 14
Minerals 2017, 7, 157 7 of 14

(b)
Figure 4. Effect of WG (n = 2.5) dosage (a) and pH (b) (c(WG) = 15mg/L) on the flotation performance
Figure 4. Effect of WG (n = 2.5) dosage (a) and pH (b) (c(WG) = 15 mg/L) on the flotation performance
mol/L).
of fluorite (c(NaOl) = 5 × 10−5 −
of fluorite (c(NaOl) = 5 × 10 5 mol/L).

3.2. Mixed Binary Mineral Flotation Results

3.2. Mixed Binary Mineral Flotation Results
From the single mineral flotation tests, adding water glass could recede the flotability of fluorite
From the single mineral flotation tests, adding water glass could recede the flotability of fluorite
and has no effect on quartz, which is not beneficial to separate them for mixed binary minerals.
and has no effect on quartz, which is not beneficial to separate them for mixed binary minerals.
However, it is simply not true. We usually add the water glass to separate fluorite and quartz ore in
However, it is simply not true. We usually add the water glass to separate fluorite and quartz ore
small scale tests or industrial tests. To explore this situation, we studied the flotation behavior of
in small scale tests or industrial tests. To explore this situation, we studied the flotation behavior of
mixed binary minerals.
mixed binary minerals.
The fluorite and quartz were mixed at the mass ratio of 1:1 with addition of WG (with different
The fluorite and quartz were mixed at the mass ratio of 1:1 with addition of WG (with different
modulus) at 15 mg/L and NaOl at 5 × 10−5 mol/L, and the results achieved are shown in Table 2. They
modulus) at 15 mg/L and NaOl at 5 × 10−5 mol/L, and the results achieved are shown in Table 2.
showed that the grade of fluorite is 61.80% and its recovery is 79.12% in the absence of water glass.
They showed that the grade of fluorite is 61.80% and its recovery is 79.12% in the absence of water
They showed that fluorite floated worse in the presence of the quartz than would have been expected
glass. They showed that fluorite floated worse in the presence of the quartz than would have been
from the results for the individual minerals. With the addition of WG, the concentration ratio
expected from the results for the individual minerals. With the addition of WG, the concentration ratio
increased as the WG modulus increased. When the modulus was 2.5, the grade of fluorite concentrate
increased as the WG modulus increased. When the modulus was 2.5, the grade of fluorite concentrate
reached 73.56%. The flotation results of the mixed binary minerals showed that the fine quartz also
reached 73.56%. The flotation results of the mixed binary minerals showed that the fine quartz also
floated and got into the concentrate in the mixed mineral flotation. The results also indicated that
floated and got into the concentrate in the mixed mineral flotation. The results also indicated that
addition of WG helped to promote the flotation separation of fluorite and quartz, and the WG with
addition of WG helped to promote the flotation separation of fluorite and quartz, and the WG with
higher modulus exhibited better separation effect.
higher modulus exhibited better separation effect.
Table 2. Flotation results of mixed binary minerals (mass ratio 1:1).
Table 2. Flotation results of mixed binary minerals (mass ratio 1:1).
WG Modulus No WG n = 1.0 n = 1.5 n = 2.0 n = 2.5 n = 3.0 n = 3.5
WG Modulus
Fluorite grade (%) 61.80 n = 1.0
No WG 65.12 n = 1.5
68.40 n =70.08
2.0 n =73.56
2.5 n 77.01
= 3.0 n79.10
= 3.5
Fluorite
Fluoriterecovery
grade (%)(%) 79.12
61.80 78.34
65.12 77.00
68.40 76.62
70.08 76.69
73.56 74.00
77.01 69.64
79.10
Fluorite recovery (%)
Concentration ratio 79.121.24 78.341.31 77.001.38 76.62
1.42 76.69
1.47 74.00
1.54 69.64
1.58
Concentration ratio 1.24 1.31 1.38 1.42 1.47 1.54 1.58

3.3. The Dispersion and Aggregation State of Mineral Particles in Pulp

3.3. The Dispersion and Aggregation State of Mineral Particles in Pulp
The optical observations on the mineral pulp in the absence and presence of flotation reagents
The opticaland
were conducted observations
the resultson
arethe mineral
shown pulp in5the
in Figures andabsence
6. and presence of flotation reagents
were conducted and the results are shown in Figures 5 and 6.
Minerals 2017, 7, 157 8 of 14
Minerals 2017, 7, 157 8 of 14

Minerals 2017, 7, 157 8 of 14

Figure 5. Dispersion and aggregation of fluorite (a), quartz (b), and mixed binary mineral (c) particles
Figure
in 5. Dispersion
distilled water. and aggregation of fluorite (a), quartz (b), and mixed binary mineral (c) particles
in distilled water.
Figure 5. Dispersion and aggregation of fluorite (a), quartz (b), and mixed binary mineral (c) particles
Figure 5 shows the dispersion and aggregation state of fine fluorite, quartz and mixed binary
in distilled water.
mineral in
Figure 5 showsthe absence of any flotation
the dispersion and reagents.
aggregation For single mineral
state of of fluoritequartz
fine fluorite, and quartz shown in
and mixed binary
Figure 5a,b,
mineral inFigure the minerals
5 showsof
the absence the
any were well
dispersion dispersed.
flotationand However,
aggregation
reagents. when fluorite
state ofmineral
For single fine fluorite,and quartz
quartz and
of fluorite were
and mixedmixed in a in
quartzbinary
shown
weight
Figure 5a,b,equivalent
mineral in the
the proportion,
absence
minerals of any
were aflotation
wellcertain aggregation
reagents.
dispersed. between
For
However, the
singlewhen two minerals
mineral was
of fluorite
fluorite and andobserved
quartzquartz
wereas shown
shown
mixed in in a
in Figure
Figure 5c.
5a,b, The
the observation
minerals were results
well indicate a
dispersed. qualitative
However, aggregation
when fluorite behavior
and in
quartz the mixed
were mixedbinary
in a
weight equivalent proportion, a certain aggregation between the two minerals was observed as shown
mineral pulp as well
weight equivalent as in the flotation
proportion, a certainpup. This is consistent
aggregation betweenwiththe twothe minerals
differencewas
in the flotation
observed as results
shown
in Figure 5c. Thesingle
between
observation results indicate a qualitative aggregation behavior in the mixed binary
in Figurethe minerals and
5c. The observation mixedindicate
results binary minerals. Therefore,
a qualitative it wasbehavior
aggregation the aggregation between
in the mixed fine
binary
mineral pulp
fluorite as well as in the flotation pup. This is consistent with the difference in the flotation results
mineraland
pulp quartz that
as well as involved the fine
in the flotation quartz
pup. Thisinto the fluorite
is consistent withconcentrate.
the difference in the flotation results
between the single
between minerals
the single mineralsand
andmixed binaryminerals.
mixed binary minerals. Therefore,
Therefore, it the
it was was the aggregation
aggregation betweenbetween
fine
fine fluorite and quartz that involved the fine quartz into the fluorite concentrate.
fluorite and quartz that involved the fine quartz into the fluorite concentrate.

Figure 6. Dispersion and aggregation of mixed binary mineral in the presence of WG with different
modulus: (a) (n = 1.0), (b) (n = 1.5), (c) (n = 2.0), (d) (n = 2.5), (e) (n = 3.0) and (f) (n = 3.5) (c(WG) = 150
mg/L,
Figurec(NaOl) = 300 mg/L).
6. Dispersion and aggregation of mixed binary mineral in the presence of WG with different
Figure 6. Dispersion
modulus: (a) (n = and
1.0), aggregation
(b) (n = 1.5), (c)of(nmixed
= 2.0), binary mineral
(d) (n = 2.5), (e) (nin= the
3.0) presence
and (f) (n =of3.5)
WG with=different
(c(WG) 150
modulus:
mg/L, (a) (n == 1.0),
c(NaOl) (b) (n = 1.5), (c) (n = 2.0), (d) (n = 2.5), (e) (n = 3.0) and (f) (n = 3.5)
300 mg/L).
(c(WG) = 150 mg/L, c(NaOl) = 300 mg/L).
Minerals 2017, 7, 157 9 of 14

Figure 6 presented a summary of the observations for the mixed binary mineral particle in the
Figure 6 presented
presence of WG a summary
with different of the
modulus. observations
The for the
results showed mixed
that, binary
as the mineral particle
WG modulus increased,in the
the
presence of WG with different modulus. The results showed that, as the WG modulus increased,
particles tended to get better dispersed. The aggregation, or the hetero-coagulation between fluorite
the
andparticles tended
quartz, was to get better
eliminated moredispersed. The WG
totally with aggregation, or the
with higher hetero-coagulation
modulus. between
It should be fluorite
noted that the
and quartz, was eliminated more totally with WG with higher modulus. It should be noted
elimination was beneficial for the flotation process, as can be seen from the flotation results in that the
elimination
Table 2. was beneficial for the flotation process, as can be seen from the flotation results in Table 2.

3.4. The Hetero-Coagulation

3.4. The Hetero-Coagulation between
between Fine
Fine Fluorite
Fluorite and
and Quartz
Quartz inin Pulp
Pulp
To
To quantify
quantify the
the hetero-coagulation
hetero-coagulation between
between fine
fine fluorite
fluorite and
and quartz
quartz in
in the
the absence
absence and
and presence
presence
of
of WG, the shear yield stress of pulp was measured. The results are shown in Figures 7 and 8.
WG, the shear yield stress of pulp was measured. The results are shown in Figures 7 and 8. ττ00 is
is
shear yield stress; it also presents a necessary force that can break this system.
shear yield stress; it also presents a necessary force that can break this system.

Figure 7. The shear strain-shear stress curves of quartz, fluorite and mixed mineral pulp in the absence
Figure 7. The shear strain-shear stress curves of quartz, fluorite and mixed mineral pulp in the absence
of flotation reagents.
of flotation reagents.

For single mineral pulp in Figure 7, the shear yield stress was 0.06 Pa for quartz and 0.63 Pa for
For The
fluorite. single mineral
results pulp inaFigure
suggested certain7,degree
the shear yield stress in
of aggregation wasthe0.06 Pa for
single quartzpulp.
minerals and 0.63 Pa for
However,
fluorite. The results suggested a certain degree of aggregation in the single minerals
for the mixed binary minerals, the shear yield stress did not locate in area of 0.06–0.63 Pa but exceeded pulp. However,
for
the the mixed
range. It canbinary minerals,
be seen that as thethe
shear yield stress
proportion did quartz
of fine not locate in area of
increased, the0.06–0.63 Pa but
shear yield exceeded
stress of the
the range. It can be seen that as the proportion of fine quartz increased,
mixed binary mineral also increased. When fluorite and quartz were mixed in a weight equivalent the shear yield stress of the
mixed binary
proportion, themineral also increased.
shear yield stress wasWhenhigh up fluorite
to 2.84 andPa,quartz werethat
indicating mixed
thein a weight equivalent
aggregation level was
proportion,
higher thanthe shear
that yield
in the stressmineral
single was high up to
pulp. The2.84increased
Pa, indicating
shear that
yieldthestress
aggregation
with fine level was
quartz
higher than that in the single mineral pulp. The increased shear yield stress
increasing in the pulp quantitatively demonstrated the strong hetero-coagulation between fine with fine quartz increasing
in the pulp
fluorite andquantitatively demonstrated
quartz in flotation pulp. the strong hetero-coagulation between fine fluorite and quartz
in flotation pulp.
The effect of WG modulus on the shear yield stress of the mixed binary mineral pulp was studied
Theresults
and the effect are
of WGshown modulus
in Figure on8.the
Asshear
the WGyield stress increased
modulus of the mixed frombinary mineral
1.0 to 3.5, pulpyield
the shear was
studied
stress ofandthe the results binary
1:1 mixed are shown in Figure
minerals 8. As
decreased fromthe 2.84
WG to modulus
0.71 Pa,increased fromthe
showing that 1.0hetero-
to 3.5,
the shear yield stress of the 1:1 mixed binary minerals decreased
coagulation between the fluorite and quartz was weakened by the WG with higher modulus. from 2.84 to 0.71 Pa, showing
that the hetero-coagulation
Combining the effect of WGbetween modulusthe on fluorite and quartz
the flotation results was weakened
in Table 2 with bythethe WG with hetero-
quantitative higher
modulus. Combining the effect of WG modulus on the flotation results in
coagulation result, it can be concluded that the WG with higher modulus helps to eliminate the Table 2 with the quantitative
hetero-coagulation
hetero-coagulationresult, between it can be concluded
fluorite and quartz.thatThis
the WGwas with higher modulus
also supported by thehelps to eliminate
optical observationsthe
hetero-coagulation
in Section 3.3. between fluorite and quartz. This was also supported by the optical observations
in Section 3.3.
Minerals 2017, 7, 157 10 of 14
Minerals 2017, 7, 157 10 of 14
Minerals 2017, 7, 157 10 of 14

Figure8.8.The
Figure Theshear
shearstrain-shear
strain-shearstress
stresscurves
curvesof
ofmixed
mixedmineral
mineral(mass
(massratio
ratioof
of1:1)
1:1)pulp
pulpin
inthe
thepresence
presence
Figure
of WG 8.(with
The shear strain-shear
different modulus) stress
at curves
150 mg/L.of mixed mineral (mass ratio of 1:1) pulp in the presence
of WG (with different modulus) at 150 mg/L.
of WG (with different modulus) at 150 mg/L.
3.5. Surface Charge and Particle Interactions between Fluorite and Quartz
3.5. Surface
3.5. Surface Charge
Charge and
and Particle
Particle Interactions
Interactions between
between Fluorite
Fluorite and
and Quartz
Quartz
In order to find out the mechanism of the hetero-coagulation, the particle interactions between
In order
order to find
find out
out the
the mechanism
mechanism of the the hetero-coagulation,
hetero-coagulation, the
the particle interactions
interactions between
between
fineIn fluorite to
and quartz were analyzed of through zeta potential resultsparticle
and calculated using DLVO
fine
fine fluorite
fluorite and quartz were analyzed through zeta potential results and calculated using DLVO
theory. The and quartz
results were analyzed
are shown in Figuresthrough
9–14. zeta potential results and calculated using DLVO
theory. The
theory. The results
results are
are shown
shown in in Figures
Figures 9–14.
9–14.

Figure 9. Zeta potential of fluorite and quartz under different pH.

Figure 9. Zeta potential of fluorite and quartz under different pH.
Figure 9. Zeta potential of fluorite and quartz under different pH.
Figure 9 shows the zeta potential of fluorite and quartz under different pH. Quartz was
Figure 9 showsacross
negatively charged the zeta the pHpotential of fluorite
range tested and quartz
but fluorite under different
was positively pH. Quartz
charged when pH waswas less
Figurecharged
negatively 9 showsacross
the zeta thepotential
pH range of tested
fluoritebut andfluorite
quartzwas
under differentcharged
positively pH. Quartz when was pHnegatively
was
than 10.0. Therefore, the electrostatic force between the two minerals when pH was less than 10less
was
charged
than 10.0.across the pH
Therefore, theto range testedforce
electrostatic but fluorite was positively charged when pH was less than
attractive. It was easy conclude that it between the two
is the attractive minerals
electrostatic when
forcepH was
that less than
contributed 10to
was the
10.0. Therefore,
attractive. It was the
easy electrostatic
to conclude force
that between
it is the the two
attractive minerals when
electrostatic pH
force was
that less than
contributed 10
to was
the
hetero-coagulation. The DLVO calculation results, including the Van der Waals’ force and the
attractive. It was easy
hetero-coagulation. The to DLVOconclude that it is
calculation the attractive
results, including electrostatic
theFigure
Van der force that contributed
Waals’ force and the to
electrostatic force, also confirmed the conclusion, as shown in 10. In this calculation, the
the hetero-coagulation.
electrostatic force, also The DLVO
confirmed calculation results, including the VanInder Waals’ force and
Hamaker constant A11 of fluorite isthe7.2 ×conclusion,
10−20 J, A22 of asquartz
shown isin
6.3Figure
× 10−20 10.
J, A33 ofthis calculation,
water is 3.7 × 10the
−20 J.
the electrostatic
Hamaker constant force,
A also
of confirmed
fluorite is 7.2 × the
10 conclusion, as shown in Figure 10. In this calculation,
−20 J, A22 of quartz is 6.3 × 10−20 J, A33 of water is 3.7 × 10−20 J.
R1 and R2 represent the radii of fluorite and quartz
11 particle, respectively. R1 and −20 R2Aareof 5 μm. The
the
R Hamaker
1 and Rpotential
constant
2 represent the Aradii
11 of of
fluorite
fluoriteis 7.2
and 10−20 J,
×quartz A22 of quartz
particle, is 6.3 ×
respectively. R110
andψR02J,2 is 33 5 μm.
are water is
surface of fluorite ψ 01 is 0.01088 V, and the quartz of surface
−20 J. R and R represent the radii of fluorite and quartz particle, respectively. R and potential −0.038 V.The
The
3.7 ×
surface10 1 2 ψ01 is 0.01088 V, and the quartz of surface potential ψ02 is −0.038 V. The2 1 R
results potential of fluorite
are calculated as follows:
results are calculated as follows:
1
= 0.461 10 1 (7)
= 0.461 10 (7)
VE equals
VE equals
Minerals 2017, 7, 157 11 of 14

are 5 µm. The surface potential of fluorite ψ01 is 0.01088 V, and the quartz of surface potential ψ02 is
−0.038 V. The results are calculated as follows:
1
Minerals 2017, 7, 157 VW = −0.461 × 103 × 11 of(7)
14
Minerals 2017, 7, 157 H 11 of 14

VE equals 1+
= 2.07 10  0.529 ln11 + + e−κH + ln 1
 (8)
= 2.07
VE = 2.07× 10
10 × −0.529
3 ln 1 −κH +
0.529× ln + ln
ln (11 − e−2κH ) (8)(8)
11 − e
and
and
and
11 1 + e−κH
 
−2κH
VTD ==−0.461
0.461× 10
3
10 × 1 + + 2.07
2.07× 10
3
10 × −0.529
0.529× ln ln1 + −κH + +ln
ln(11 − e ) (9)
(9)
= 0.461 10 H + 2.07 10 0.529 ln 1 − e + ln 1 (9)
1
It can be seen from Figure 10 that the value of of V W,, V
VW and VTD were
VEEand were always
always negative,
negative, suggesting
It can be seen from Figure 10 that the value of V W, VE and were always
the attractive interaction energy between fluorite and quartz particles. The calculations negative,
calculations alsosuggesting
indicated
indicated
the attractive
that ititwas interaction
wasthethe
attractive energy between
interaction
attractive fluorite
between
interaction and quartz
the fluorite
between particles.
and quartz
the fluorite The
and that calculations
causes
quartz also
thecauses
that indicated
hetero-coagulation
the hetero-
that
and it
then was the
involved attractive
the fine interaction
quartz into between
the fluoritethe fluorite
concentrate. and
coagulation and then involved the fine quartz into the fluorite concentrate. quartz that causes the hetero-
coagulation and then involved the fine quartz into the fluorite concentrate.

Figure 10. The relationship between interaction energy of fluorite and quartz and particles distance
Figure 10.
Figure The relationship
10. The relationship between
betweeninteraction
interactionenergy
energyof
of fluorite
fluorite and
and quartz
quartz and
and particles
particles distance
distance
(pH = 7).
(pH = 7).
(pH = 7).

Figure 11. Zeta potential of fluorite and quartz with WG under different pH (c(WG) = 5 × 10−5 mol/L
Figure
Figure
(n 11.
11. Zeta
= 2.5)). Zeta potential
potential of
of fluorite and quartz
fluorite and quartz with
withWG
WGunder
underdifferent
differentpH
pH(c(WG) 10−−55 mol/L
(c(WG)= =5 5××10 mol/L
(n
(n==2.5)).
2.5)).
Figure 11 shows the zeta potential of fluorite and quartz in the presence of WG under different
Figure 11 shows
pH. Compared thezeta
with the zetapotential
potentialresults
of fluorite and 9,
in Figure quartz in the
the zeta presence
potential of WG was
of fluorite under different
remarkably
pH. Compared
decreased with
by the the zeta
addition ofpotential results in
WG. However, theFigure
change9, the zetapotential
in zeta potentialof
ofquartz
fluoritewaswasinsignificant.
remarkably
decreased by the addition
The results of VW, VE and of WG. However, the change in zeta potential of quartz was
as a function of h when pulp pH was 7 were shown in Figure 12. The insignificant.
The results of V W, VE and as a function
results indicated that with the addition of WG,of hthe
when pulp pH was
Van-der-Waals 7 were
energy was shown in Figurehowever,
still negative; 12. The
results indicated energy
the electrostatic that with the addition
changed of WG,As
to positive. thea Van-der-Waals
result, an energy energy was
barrier still×negative;
(2.22 10−3 KT) however,
emerged,
the electrostatic energy changed to positive. As a result, an energy barrier (2.22 × 10−3 KT) emerged,
Minerals 2017, 7, 157 12 of 14

Figure 11 shows the zeta potential of fluorite and quartz in the presence of WG under different
pH. Compared with the zeta potential results in Figure 9, the zeta potential of fluorite was remarkably
decreased by the addition of WG. However, the change in zeta potential of quartz was insignificant.
The results of VW , VE and VTD as a function of h when pulp pH was 7 were shown in Figure 12.
The results indicated that with the addition of WG, the Van-der-Waals energy was still negative;
however, the electrostatic energy changed to positive. As a result, an energy barrier (2.22 × 10−3 KT)
emerged,
Mineralsshowing
2017, 7, 157 that the hetero-coagulation between fluorite and quartz could be hindered12 of 14 if the
kinetic energy
Minerals 2017,could
7, 157 not come over the barrier. The results showed that the addition of WG12 could
of 14 help
energy
depress the could not come over between
hetero-coagulation the barrier. The results
fluorite showed
and quartz in that the addition
flotation pulp. of WG could help
depresscould
energy the hetero-coagulation
not come over thebetween
barrier.fluorite and quartz
The results showedin flotation
that the pulp.
addition of WG could help
depress the hetero-coagulation between fluorite and quartz in flotation pulp.

Figure 12. The interaction energy of fluorite and quartz particles with addition of WG (n = 2.5, c(WG)
Figure 12. −5The interaction energy of fluorite and quartz particles with addition of WG (n = 2.5,
= 5 × 1012.mol/L,
Figure pH = 7) asenergy
The interaction a function of particle
of fluorite and distance.
quartz particles with addition of WG (n = 2.5, c(WG)
c(WG) = 5 × 10−5 mol/L, pH = 7) as a function of particle distance.
= 5 × 10 mol/L, pH = 7) as a function of particle distance.
−5

Figure 13. Zeta potential of fluorite and quartz with the addition of WG with different modulus
(c(WG) 13.
Figure = 5 ×Zeta mol/L). of fluorite and quartz with the addition of WG with different modulus
10−5 potential
Figure 13. Zeta potential of fluorite and quartz with the addition of WG with different modulus
105 mol/L).
(c(WG) = 5 × − −5
(c(WG) 5 × 10
The= zeta mol/L).
potential of fluorite and quartz with the addition of WG with different modulus was
measured andpotential
The zeta the results are shown
of fluorite andinquartz
Figurewith
13. the
Theaddition
results showed that as
of WG with the modulus
different modulus of was
WG
increased,
measured the surfaces
The zeta potential
and of of
the results both
fluorite minerals
and in
are shown were with
quartz
Figuremore negatively
the
13. The addition
results charged.
of WG
showed For fluorite,
with
that as whenmodulus
different
the modulus the
of WG was
modulus
increased,
measured was
and the
the1.0, the zeta
surfaces
results of
arepotential
both was
minerals
shown −14.6
weremV.
in Figure 13.When
more the
negatively
The WGcharged.
results modulus
showed was
For 3.5,
as the
fluorite,
that zeta
thewhen potential
the WG
modulus of WG
was −37.2
modulus mV.
was For
1.0, quartz,
the zeta when
potentialthe
wasWG modulus
−14.6 mV. was
When 1.0,
the the
WG zeta potential
modulus
increased, the surfaces of both minerals were more negatively charged. For fluorite, when was was
3.5, −35.6
the mV.
zeta When
potentialthe WG
the WG
was −37.2modulus
mV.theForincreased
quartz, to 3.5,
when thethe zeta potential increased to −60.3 mV. The effect of the WG
modulus was 1.0, zeta potential wasWG modulus
−14.6 was
mV. When 1.0, the
the WG zeta potential
modulus was 3.5,
was −35.6 mV.
the zetaWhenpotential
modulus
the on the interaction
WG modulus increasedenergy
to 3.5, between the fluorite
the zeta potential and quartz
increased can be
to −60.3 seen
mV. Thein Figure 14.the
effect of AsWGthe
was −37.2 mV. For quartz, when the WG modulus was 1.0, the zeta potential was −35.6 ×mV. When the
WG modulus
modulus on theincreased fromenergy
interaction 1.0 to 3.5, the energy
between barrierand
the fluorite increased
quartz from 0.94
can be × 10
seen to 6.1114.
in−3Figure 10As
−3 KT.
the
WG modulus
The modulus increased
results demonstrate to 3.5, thethe
that zeta potentialeffect
increased −60.3
toWG mV.hetero-coagulation
The effect of the WG−3 modulus
WG increased from 1.0 todepression of theincreased
3.5, the energy barrier on from
the 0.94 × 10−3 to 6.11 ×between
10 KT.
on the
The interaction
fluorite
results energy
and demonstrate
quartz between
was modulus the fluorite
that the dependent.
depression WG and ofquartz
with
effect higher
the WGcanon be
theseen
modulus in Figure
exhibited more14.
hetero-coagulation As the WG
depression
between
modulus × 10 −3 to 6.11 × 10−3 KT.
effect increased
fluoriteonand
the quartz from
was1.0
hetero-coagulation to 3.5,between
modulus the energy barrier
fine WG
dependent. fluorite increased
withand quartz
higher fromtherefore,
and
modulus 0.94
exhibited improved more on
more depression
the flotation
effect on the selectivity.
hetero-coagulation between fine fluorite and quartz and therefore, improved more on
the flotation selectivity.
Minerals 2017, 7, 157 13 of 14

The results demonstrate that the depression effect of the WG on the hetero-coagulation between
fluorite and quartz was modulus dependent. WG with higher modulus exhibited more depression
effect on the hetero-coagulation between fine fluorite and quartz and therefore, improved more on the
flotation selectivity.
Minerals 2017, 7, 157 13 of 14

Figure 14. The interaction energy of fluorite and quartz particles with addition of WG with different
Figure 14. The interaction energy of fluorite and quartz particles with addition of WG with different
modulus (c(WG) = 5 × 10−5 mol/L, pH = 7) as a function of particle distance.
modulus (c(WG) = 5 × 10−5 mol/L, pH = 7) as a function of particle distance.
4. Conclusions
4. Conclusions
Given the aforementioned results, we arrived at the following primary conclusions:
Given the aforementioned
(1) Fluorite readily floats butresults, we arrived
quartz does not floatatusing
the following primary
sodium oleate conclusions:
as collector;
(2) There exists strong hetero-coagulation between fine fluorite and quartz which decreases the
(1) Fluorite readily floats but quartz does not float using sodium oleate as collector;
flotation selectivity to a large extent;
(2) There exists strong hetero-coagulation between fine fluorite and quartz which decreases the
(3) The addition of water glass helps to depress the hetero-coagulation and then improves the
flotation selectivity
separation to ainlarge
efficiency extent;
flotation of mixed binary minerals;
(3) The Water
(4) addition
glassofwith
water glass
higher helps eliminates
modulus to depressthethe hetero-coagulation
hetero-coagulation more and then improves
thoroughly through the
separation efficiency
increasing the energyin flotation of mixed
barrier between finebinary
fluoriteminerals;
and quartz.
(4) Water glass
At the with
same higher
time, modulus
the actual eliminates
flotation the hetero-coagulation
tests on fluorite-quartz more
ore showed that thethoroughly through
grade of fluorite
increasing the energy barrier between fine fluorite and quartz.
can increase from 19.26% to 25.99% with increasing the WG modulus from 1.0 to 3.5 in the absence
of other flotation reagents, which indicated that conclusions can apply to the industrial application
At theflotation
in the same time, the actual
of fluorite flotation
and quartz ore.tests on fluorite-quartz
The future oreresearches
direction of the showed that
wouldthefocus
grade
onof fluorite
how
can increase from 19.26% to 25.99% with increasing the WG modulus from 1.0 to 3.5 in
to eliminate the hetero-coagulation to the maximum, for example, adding metal ion into water glass the absence of
otherand
flotation reagents, which
developing new depressants. indicated that conclusions can apply to the industrial application in
the flotation of fluorite and quartz ore. The future direction of the researches would focus on how to
Acknowledgments:
eliminate This work was
the hetero-coagulation financially
to the maximum,supported by the Major
for example, State metal
adding Basic Research
ion intoDevelopment
water glass and
Program of China (973 Program), the Innovation Driven Plan of Central South University (Grant No.
developing new depressants.
2015CX005), and the Collaborative Innovation Center for Clean and Efficient Utilization of Strategic Metal
Mineral Resources.
Acknowledgments: This work was financially supported by the Major State Basic Research Development Program
of China (973Contributions:
Author Program), the Innovation Driven Plan
Wei Chen designed the of Central South
experiment; University
Yawen Gao and(Grant
Dezhi No.
Liu 2015CX005), and the
performed the
Collaborative Innovation
experiments, collectedCenter for Clean
all the data and this
and wrote Efficient
paper.Utilization of Strategic
Guofan Zhang analyzedMetal Mineral
the data Resources.
and involved in the
discussion of the results and approved reading the manuscript.
Author Contributions: Wei Chen designed the experiment; Yawen Gao and Dezhi Liu performed the experiments,
collected all theofdata
Conflicts and The
Interest: wrote this paper.
authors declareGuofan Zhang
no conflict analyzed the data and involved in the discussion of the
of interest.
results and approved reading the manuscript.
References
Conflicts of Interest: The authors declare no conflict of interest.
1. Beger, J.; Schmidt, C.; Szymanowskib, J.; Barhoum, R. Surface activity and fluorite flotation with myristic
References
acid derivatives containing oxygen and sulphur atoms. Colloids Surf. A Physicochem. Eng. Asp. 1993, 80, 197–201.
2. Zhang, Y.; Song, S. Beneficiation of fluorite by flotation in a new chemical scheme. Miner. Eng. 2003, 16,
1. Beger, J.; Schmidt, C.; Szymanowskib, J.; Barhoum, R. Surface activity and fluorite flotation with myristic
597–600.
acid Free,
3.
derivatives containing oxygen and sulphur atoms. Colloids Surf. A Physicochem. Eng. Asp. 1993, 80,
M.L.; Miller, J.D. The significance of collector colloid adsorption phenomena in the fluorite/oleate
197–201. [CrossRef]
flotation system as revealed by FTIR/IRS and solution chemistry analysis. Int. J. Miner. Process. 1996, 48,
197–216.
Minerals 2017, 7, 157 14 of 14

2. Zhang, Y.; Song, S. Beneficiation of fluorite by flotation in a new chemical scheme. Miner. Eng. 2003, 16,
597–600. [CrossRef]
3. Free, M.L.; Miller, J.D. The significance of collector colloid adsorption phenomena in the fluorite/oleate
flotation system as revealed by FTIR/IRS and solution chemistry analysis. Int. J. Miner. Process. 1996, 48,
197–216. [CrossRef]
4. Fa, K.; Nguyen, A.V.; Miller, J.D. Interaction of calcium dioleate collector colloids with calcite and fluorite
surfaces as revealed by AFM force measurements and molecular dynamics simulation. Int. J. Miner. Process.
2006, 81, 166–177. [CrossRef]
5. Schubert, H.; Baldauf, H.; Kramer, W.; Schoenherr, J. Further development of fluorite flotation from ores
containing higher calcite contents with oleoylsarcosine as collector. Int. J. Miner. Process. 1990, 30, 185–193.
[CrossRef]
6. Irannajad, M.; Ejtemaei, M.; Gharabaghi, M. The effect of reagents on selective flotation of
smithsonite–calcite–quartz. Miner. Eng. 2009, 22, 766–771. [CrossRef]
7. Zhou, W.; Moreno, J.; Torres, R.; Valle, H.; Song, S. Flotation of fluorite from ores by using acidized water
glass as depressant. Miner. Eng. 2013, 45, 142–145. [CrossRef]
8. Zhu, Y.; Zhu, J. Chemical Principle of Flotation Regents; Central South University of Technology Press: Changsha,
China, 1996.
9. Nordström, J.; Sundblom, A.; Jensen, G.V.; Pedersen, J.S.; Palmqvist, A.; Matic, A. Silica/alkali ratio
dependence of the microscopic structure of sodium silicate solutions. J. Colloid Interface Sci. 2013, 397,
9–17. [CrossRef] [PubMed]
10. Arantes, R.S.; Lima, R.M.F. Influence of sodium silicate modulus on iron ore flotation with sodium oleate.
Int. J. Miner. Process. 2013, 125, 157–160. [CrossRef]
11. Zhang, G.F.; Cui, M.M.; Zhu, Y.G.; Shi, Q.; Luo, N. Effect of water glass on flotation separation of smithsonite
and quartz. Chin. J. Nonferr. Met. 2012, 22, 3535–3540.
12. Al-Thyabat, S. Empirical evaluation of the role of sodium silicate on the separation of silica from Jordanian
siliceous phosphate. Sep. Purif. Technol. 2009, 67, 289–294. [CrossRef]
13. Ou, L.M.; Huang, S.J.; Zhu, Y.G. Influence of metal ions on floatability of quartz in flotation of sulfide ores.
J. Cent. South Univ. Sci. Technol. 2012, 43, 3–7.
14. Kou, J.; Xu, S.; Sun, T.; Sun, C.; Guo, Y.; Wang, C. A study of sodium oleate adsorption on Ca2+ activated
quartz surface using quartz crystal microbalance with dissipation. Int. J. Miner. Process. 2016, 154, 24–34.
[CrossRef]
15. Fornasiero, D.; Ralston, J. Cu(II) and Ni(II) activation in the flotation of quartz, lizardite and chlorite. Int. J.
Miner. Process. 2005, 76, 75–81. [CrossRef]
16. GÜler, T.; Akdemir, Ü. Statistical evaluation of flotation and entrainment behavior of an artificial ore.
Trans. Nonferr. Met. Soc. China 2012, 22, 199–205. [CrossRef]
17. Gong, J.; Peng, Y.; Bouajila, A.; Ourriban, M.; Yeung, A.; Liu, Q. Reducing quartz gangue entrainment in
sulphide ore flotation by high molecular weight polyethylene oxide. Int. J. Miner. Process. 2010, 97, 44–51.
[CrossRef]
18. Kirjavainen, V.M. Review and analysis of factors controlling the mechanical flotation of gangue minerals.
Int. J. Miner. Process. 1996, 46, 21–34. [CrossRef]
19. Cruz, N.; Peng, Y. Rheology measurements for flotation slurries with high clay contents—A critical review.
Miner. Eng. 2016, 98, 137–150. [CrossRef]
20. Liang, L.; Peng, Y.; Tan, J.; Xie, G. A review of the modern characterization techniques for flocs in mineral
processing. Miner. Eng. 2015, 84, 130–144. [CrossRef]
21. Zhang, W.; Honaker, R.; Li, Y.; Chen, J. The importance of mechanical scrubbing in magnetite-concentrate
reverse-flotation. Miner. Eng. 2014, 69, 133–136. [CrossRef]

© 2017 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).