minerals

Article
Spodumene Flotation Mechanism
Lev Filippov 1,2 , Saeed Farrokhpay 1, * , Lichau Lyo 1 and Inna Filippova 1
1 Université de Lorraine, CNRS, GeoRessources, Nancy F-54000, France; lev.filippov@univ-lorraine.fr (L.F.);
lichau.lyo@univ-lorraine.fr (L.L.); inna.filippova@univ-lorraine.fr (I.F.)
2 National University of Science and Technology MISIS, Moscow 119049, Russia
* Correspondence: saeed.farrokhpay@univ-lorraine.fr; Tel.: +33372744535




Received: 23 April 2019; Accepted: 11 June 2019; Published: 21 June 2019


Abstract: Fine and coarse fractions of spodumene were obtained from a pegmatite ore and their
flotation was investigated under different conditions. In particular, the optimum pH and collector
dosage were studied. It was found that the best flotation performance occurs at pH 10 using 250 mg/L
of sodium oleate. It was also observed that upon the addition of CaCl2 , spodumene flotation recovery
increases to about 90%. In addition, poor floatability was found for spodumene when Na2 CO3 was
used as a pH regulator (compared to NaOH).The zeta potential data confirmed the adsorption of
oleate on the spodumene surface. It was found that activation of spodumene by calcium ions makes
the surface charge less negative due to the adsorption of Ca2+ on the surface. The crystallographic
properties of spodumene were analyzed. The adsorption of sodium oleate was attributed to the
chemisorption of oleate to the exposed Al and Si sites generated after breakage of the Al–O and Si–O
bonds on the mineral surface. It was observed that the {110} planes are the most favorable for the
adsorption of oleate. The {110} plane is the weakest plane, and spodumene has the highest tendency
to cleave along this plane. The XRD data revealed that fine spodumene particles have more {110}
planes than the coarser fraction, which may explain why the former has better floatability.

Keywords: lithium; spodumene; flotation; sodium oleate

1. Introduction
Lithium is widely used in batteries, ceramics, glass, lubricants, refrigeration and the nuclear and
optoelectronics industries. With the development of computers, digital cameras, mobile phones and
other electronic devices, the battery industry has become the largest consumer of lithium. The lithium
market has grown dramatically in recent years. The total global consumption of lithium almost doubled
in 2016 compared to 2008, due mainly to the development of the lithium-ion battery market [1]. It is
expected that the lithium demand to be increased at an average annual growth rate of 10% over the
next decade [2], and the supply of lithium should increase accordingly.
Around 150 different minerals contain lithium and approximately 30 of these have a significant
quantity of lithium. However, only five of these minerals have economic value. They include
spodumene (LiAlSi2 O6 ) from the pyroxene sub-group, lepidolite (KLiAl1,5 Li1,5 (Si3 Al10 )(F)2 ) and
zinnwaldite (KLiFeAl(AlSi3 )O10 (OH,F)2 ) from the mica family, petalite (LiAlSi4 O10 , tectosilicate) and a
lithium phosphate-amblygonite ((Li,Na)AlPO4 (F,OH)). Spodumene contains approximately 8% Li2 O
which is the most abundant lithium-containing mineral. Due to the similarity of the physical-chemical
properties of lithium minerals (including spodumene) and their associated gangue minerals (e.g., quartz,
feldspar, mica), it is often challenging to separate lithium minerals [3]. The typical beneficiation methods
consist of flotation, hand sorting, heavy media separation, thermal treatment and magnetic separation.
Flotation is the most widely used beneficiation method for lithium minerals, including spodumene.
While sodium oleate is often used as a collector in spodumene flotation, recent studies have suggested

Minerals 2019, 9, 372; doi:10.3390/min9060372 www.mdpi.com/journal/minerals

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Minerals 2019, 9, x FOR PEER REVIEW 2 of 12

new collector mixtures for this purpose [4,5]. The characteristic surface crystal chemistry of spodumene
has been determined
chemistry of spodumene to behas
thebeen
maindetermined
contributing to factor
be theinmain
spodumene selective
contributing flotation
factor with an
in spodumene
oleate collector
selective when
flotation withother aluminosilicates,
an oleate collector when such as aluminosilicates,
other muscovite, quartzsuch andas feldspar, are present
muscovite, [6].
quartz and
Investigations of the crystallography of spodumene have become more important.
feldspar, are present [6]. Investigations of the crystallography of spodumene have become more As shown in
Figure 1, each of the individual tetrahedrons in a single-chain of silicates faces
important. As shown in Figure 1, each of the individual tetrahedrons in a single-chain of silicates the same direction.
These chains
faces the sameof direction.
silicate tetrahedrons
These chainsareofbound together
silicate laterally
tetrahedrons arethrough
bound ionic
together bonding withthrough
laterally Li and
Al in octahedral coordinates, leading to a unit cell formula of Li Al Si(O ) . The Al 3+ sites on the
ionic bonding with Li and Al in octahedral coordinates, leading to4a unit 4 3 8formula of Li4Al4Si(O3)8.
cell
spodumene surface have specific interactions with different chemical
The Al sites on the spodumene surface have specific interactions with different
3+ reagents, as ischemical
discussed further
reagents,
in this paper.
as is discussed further in this paper.

Figure 1. The crystallographic structure of spodumene [7].

Moon and Fuerstenau [6] studied the surface chemistry of spodumene when oleate is present in
order to understand the crystallographic difference between spodumene and other aluminosilicates. aluminosilicates.
They found that the surface Al site is the most favorable site for the selective selective chemisorption
chemisorption of of oleate.
oleate.
In fact, Al sites in other aluminosilicates
other aluminosilicates are deeply
deeply buried inside the crystal unit, making them
buried inside the crystal unit, making them
unavailable
unavailable forfor oleate
oleateadsorption.
adsorption.They Theyalso
alsocalculated
calculated thethe broken
broken ionic
ionic bondbond strength
strength perper
unitunit
areaarea
for
for
the the {110},
{110}, {010},{010},
{001}{001} and {100}
and {100} cleavagecleavage
planesplanes
as 2.521 as×2.521 × 1014
1014, 3.155 × ,103.155 × 10×1410
14, 4.165 and ×
, 144.165 1014× and
4.570 1014
4.570 × 10142, valence/cm
valence/cm respectively. 2 , respectively. This indicates that cleavage occurs along the weakest {110}
This indicates that cleavage occurs along the weakest {110} plane. Zhu et al. [8]
plane. Zhu et al.
also reported [8] also
that, while reported
the fourthat, while the four
spodumene spodumene
surfaces surfaces
({110}, {010}, {001}({110},
and{010},
{100}){001}are and {100})
naturally
are naturally hydrophilic, the preferential adsorption of sodium oleate on
hydrophilic, the preferential adsorption of sodium oleate on the {100} and {110} surfaces makes them the {100} and {110} surfaces
makes them hydrophobic.
hydrophobic.
The spodumene
spodumene surface surfacegenerally
generallyhas hasa anegative
negative zetazeta potential
potential in solutions
in solutions of pH of >pH > 3This
3 [9]. [9].
This indicates that the separation of spodumene could be
indicates that the separation of spodumene could be possible using cationic possible using cationic collectors. Amine
collectors are the main cationic collectors used in spodumene flotation, and are normally applied in
reverse flotation to floatfloat thethe gangue
gangue minerals
minerals (e.g.,
(e.g., quartz,
quartz, mica
mica or
or feldspar).
feldspar). The performance
performance of
sodium oleate
oleate and
and lauryl
laurylamine
amineas ascollectors
collectorsininspodumene
spodumeneflotation
flotationhas hasbeen beeninvestigated
investigated [10]
[10]and
and it
was found
it was found that
thatlauryl
laurylamine
amineachieves
achievesa ahigher
higherrecovery
recoveryof ofspodumene
spodumenethan than sodium
sodium oleate (i.e., 90%
vs. 50%,
50%, respectively).
respectively). Although
Although the the clean
clean surface
surface ofof spodumene
spodumene is is negatively
negatively charged charged at pH > > 3,
there are normally + 3+
normally several
several cationic
cationic ions
ions suspended
suspended in inthe
thesolution,
solution,suchsuchas asLiLi and
+ andAl Al , which can
3+

attach to the clean surface

surface and and easily
easily form
form aa bond
bond with
with the the anionic
anionic collectors.
collectors. This is probably the
reason for the
the wide
wide utilization
utilization of of anionic
anionic collectors
collectors in in spodumene
spodumene flotation.
flotation. As stated above, oleic
acid is the
the most
most frequently
frequently used used anionic
anionic collector
collector in
in spodumene
spodumene flotation.
flotation. Oleic acid performs best
under
under slightly
slightly alkaline
alkaline conditions
conditions(pH (pH== 8–9).
8–9). As oleic acid forms RCOO−− ions ions atat aa strong
strong alkaline
alkaline pH,
pH,
and ROOH at acidic and neutral pH levels, both exist under a slightly alkaline pH and tend to form
an ion-molecule complex. The RCOO−− group group will
will react
react with
with the positive Al ions on the spodumene
surface generated through chemical bonding. Meanwhile, Meanwhile, the presence of molecular oleic acid will
increase the negative value of the charge of RCOO−, which strengthens the chemical bonding and
increases its hydrophobicity [11].
Minerals 2019, 9, 372 3 of 11

increase the negative value of the charge of RCOO− , which strengthens the chemical bonding and
increases its hydrophobicity [11].
It is acknowledged that many studies have been carried out to improve spodumene flotation.
However, most of the published papers focus on using different reagents, and the flotation mechanism
is not yet fully understood. In this study, the flotation behavior of spodumene (obtained from a
pegmatite ore) with different particle sizes was studied to determine the optimum flotation particle
size range. This provides a theoretical basis for the selective grinding of spodumene. In addition,
the optimum flotation conditions of spodumene is determined in order to improve the efficiency of
flotation. Finally, the mechanism of spodumene flotation is discussed in conjunction with its surface
charge behavior and its crystallography. The results of this study could have a significant effect on
future productions of spodumene, and therefore could be of economic importance.

2. Materials and Experimental Methods

Spodumene was prepared from Länttä pegmatite ore deposit in Finland. The main minerals in
the ore were identified as spodumene, quartz, muscovite, albite and potassium feldspar. The lumpy
spodumene-rich pegmatite ore particles were manually selected from the batch rocks. The ore was
crushed to less than 2 mm. Due to the density difference between spodumene and the gangue minerals,
heavy media separation was performed to separate the spodumene. The gangue minerals present in
the ore have densities of about 2.70 g/cm3 while the density of spodumene is about 3.20 g/cm3 [12].
The dense media used in this study was a mixture of bromoform and tetra-bromoform with a density
of 2.95 g/cm3 . The heavy fraction was dried at 50 ◦ C and then ground to less than 700 µm. Another
stage of heavy media separation was conducted to remove fine gangue particles and impurities. Finally,
the desired size fractions were obtained after grinding and sieving.
XRD measurements were conducted to analyze the composition of the prepared spodumene
samples and extract structural information. The measurements were performed on a Bruker D8
ADVANCE diffractometer with CuKα radiation (wavelength = 17.8897 nm). The XRD data were
processed using DIFFFRAC.EVA provided by Bruker.
Scanning electron microscopy (SEM) was used to scan surface of the samples. Various signals
generated by the interactions between the electrons and atoms contain information on the sample
topography and composition. The machine used was a Hitachi S-4800 (Tokyo, Japan), which features a
resolution down to 1 nm at 15 kV with acceleration tension between 0.1 and 30 kV.
Zeta potential measurements were performed using a Zetameter IV (CAD Instruments, France).
Generally, particles have different movements in the presence of an electric field. Thus, the surface
charge can be calculated according to this movement when combined with knowledge of the electric
field magnitude, mobility velocity and direction. Using an agate mortar, 1 g of spodumene was
ground to below 5 µm and stored in a glass bottle. The amount of sample used for each test was
50 mg with 200 mL of NaNO3 electrolyte solution. Each sample was stirred for 3 min to obtain a
stable dispersion. The pH regulators were dilute solutions of HCl or NaOH. After the desired pH was
obtained, the collector was added to the solution when needed. Finally, the suspension was injected
into the apparatus using a syringe to test the electrophoretic mobility of the particles. Each test was
repeated at least three times.
Flotation tests were performed using a Hallimond tube. One g of spodumene sample was
suspended in 300 mL of deionized water and the reagents were then added and rotated with a magnetic
stirrer for 30 s. Nitrogen gas was introduced at the volume rate of 60 mL/min. Sodium oleate (NaOl)
was used as a collector (250 mg/L, as reported by Liu et al. [9]). The optimum collector dosage was also
reconfirmed in the initial tests since the spodumene recovery increased as the NaOl dosage increased
up to 250 mg/L, and was unchanged after that. Flotation tests were carried out for 10 min with agitation
at 500 rpm.
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3. Results and Discussion
recovery is a bit higher for almost all pH ranges for the finer fraction (i.e., the 40–80 μm compared to
In theμm
the 80–150
Minerals initial
9, xtests,
2019,fraction), the
FOR PEER spodumene
as REVIEW flotationlater
is further discussed recovery
in thisincreased
paper. as the pH was raised from 2 to 10,
4 of 12
and then stayed more or less unchanged up to pH 12 (Figure 2). Figure 2 also shows that the flotation
recovery
recovery is a is
bita higher
bit higherforfor almostall
almost allpH
pHranges
ranges for
for the
thefiner
finerfraction (i.e.,
fraction thethe
(i.e., 40–80 μm compared
40–80 to
µm compared to
the 80–150 μm fraction), as is further 80-150 μm
discussed later in this 40-80
paper.μm
the 80–150 µm fraction), as is further discussed later in this paper.
100
90 80-150 μm 40-80 μm

80 100
70 90
80
Recovery %

60
70
50
Recovery %

60
40
50
30 40
20 30
10 20
0 10
00 2 4 6 8 10 12
0 2 4 6
pH 8 10 12
pH
Figure 2. Effect of pH on spodumene flotation for the coarse and fine fractions.
Figure 2. Effect
Figure ofof
2. Effect pHpHon
onspodumene flotationfor
spodumene flotation forthe
thecoarse
coarse and
and finefine fractions.
fractions.

As shown in Figure 3, the isoelectric point (i.e.p.) of spodumene is at approximately pH 2, which

As shown
As shown in Figure
in Figure3, the isoelectric
3, the isoelectricpoint
point (i.e.p.)
(i.e.p.) ofofspodumene
spodumene is approximately
is at at approximately pH 2,pH 2, which
which
is in agreement withwith
the previously reported data (e.g., Xu
Xu et al. [10]).The The zeta potential becomes
is in is in agreement
agreement with thethe previouslyreported
previously reported data
data (e.g.,
(e.g., Xuetetal.al.[10]).
[10]). The zetazeta
potential becomes
potential becomes
more more
negative as the
negative pHpH
as the increases
increases upuptotopH pH10,
10, at
at which point
pointititbecomes
becomes less negative (Figure2). 2).
more negative as the pH increases up to pH 10, at which
which point it becomes less negative
less negative(Figure
(Figure 2).
This is similar to the flotation recovery
recoveryresults
results seen
seen at differentpH pH levels. In In fact,
the the maximum
This This is similar
is similar to the
to the flotation
flotation recovery results seen at
at different
different pHlevels. levels. fact,
In fact, maximum
the maximum
flotation recovery
flotation waswas
recovery obtained
obtained at at
pH pH 10,
10,when
whenspodumene
spodumene isishighly
highlynegatively
negatively charged.
charged. At this
At this pH, pH,
flotation recovery was obtained at pH 10, when spodumene is highly negatively charged. At this pH,
the spodumene
the spodumene surface is capable
surface is capable of of
thethemaximum
maximumnumber number of ofinteractions
interactions with
with thethe positively
positively charged
charged
the spodumene surface is capable of the maximum number of interactions with the positively charged
sites. sites. It should
It should be noted
be noted thatthat
thethe zetapotential
zeta potentialof of the
the cleaned
cleanedspodumene
spodumene surface
surface is different fromfrom
is different
sites.that
It should
of the be noted that
non-cleaned the (Figure
surface zeta potential
3). of thecontaminants
Therefore, cleaned spodumenecan affect surface
the surfaceis different
charge of from
that of the non-cleaned surface (Figure 3). Therefore, contaminants can affect the surface charge of
that of the non-cleaned
spodumene surface (Figure 3). Therefore, contaminants can affect necessary
the surface charge of
spodumene and,and, consequently,
consequently, itsits interactions
interactions with other
with other reagents.
reagents.ItItis istherefore
therefore necessaryto clean
to clean
spodumene and, consequently,
the spodumene surface before itsflotation.
interactionsThe with other reagents.
zeta potential data for Itthe is therefore
acid-cleaned necessary
sample are to clean
the spodumene surface before flotation. The zeta potential data for the acid-cleaned sample are
the spodumene
similar to thosesurface before
reported flotation.
in the literatureThe zetaXupotential
(e.g., data for the acid-cleaned sample are similar
et al. [13]).
similar to those reported in the literature (e.g., Xu et al. [13]).
to those reported in the literature (e.g., Xu et al. [13]).
Non acid cleaned sample Acid cleaned sample
Non acid cleaned sample Acid cleaned sample
20
20
0
0 0 2 4 6 8 10 12
Zeta Potential (mv)

-20
0 2 4 6 8 10 12
Zeta Potential (mv)

-20 -40

-40 -60

-60 -80

-80-100
-120
-100
pH
.
-120
pHnon-cleaned and cleaned spodumene.
Figure 3. Comparison of the zeta potentials of
.
Figure 3. Comparison of the zeta potentials of non-cleaned and cleaned spodumene.
Figure 3. Comparison of the zeta potentials of non-cleaned and cleaned spodumene.
Minerals 2019, 9, 372 5 of 11
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Minerals 2019, 9, x FOR PEER REVIEW 5 of 12
When the collector (i.e., NaOl) is added, the zeta potential of spodumene becomes more negative
Whenthe
When thecollector
collector (i.e.,
(i.e., NaOl)
NaOl) is added,
is added, thepotential
the zeta zeta potential of spodumene
of spodumene becomes becomes
more more negative
negative
over a wide pH range (Figure 4), demonstrating that collector adsorption indeed occurs. The zeta
over
over aapotential
widepH
wide pH range (Figure 4), demonstrating that collector adsorption indeed
of the spodumene particles becomes even more negative when the dosage of NaOlzeta
range (Figure 4), demonstrating that collector adsorption indeed occurs. occurs.
The The zeta
increases
potential
potential of the
of the
(Figure spodumene
4). spodumene particles
The ion-molecule becomes
particles even
becomes
complexes more
even
react negative
withmore when the
negativeAlwhen
the exposed dosage of
thethe
sites on NaOl
dosage increases
of NaOl
spodumene increases
surface,
(Figure
(Figure 4).
4).The
Theion-molecule
reducing ion-molecule
the complexes
positive charge on thereact
complexes with with
react
spodumene thesurface
exposed Altherefore
the exposed
and sitesAl
onsites
the spodumene
on thethe
decreasing surface,
spodumene
zeta surface,
potential.
reducing the
reducing thepositive
positive charge
charge ononthethe
spodumene
spodumenesurface and therefore
surface decreasing
and therefore the zeta the
decreasing potential.
zeta potential.
20
20
0
0 0 2 4 6 8 10 12
Zeta potential (mV)

0 -20 2 4 6 8 10 12
Zeta potential (mV)

-20
-40
-40 No NaOl
-60 No NaOl
-60 10-6 NaOl
-80 10-6 NaOl
-80 10-4 NaOl
10-4 NaOl
-100
-100
-120
-120 pH
pH

Figure 4. Effects of NaOl on the zeta potential of spodumene under different pH conditions.
Figure 4. Effects of NaOl on the zeta potential of spodumene under different pH conditions.
Figure 4. Effects of NaOl on the zeta potential of spodumene under different pH conditions.
Based on the initial results, the highest recovery for spodumene flotation is still less than 70%
Based on the initial results, the highest recovery for spodumene flotation is still less than 70%
(Figure
Based2). on
The theflotation
initial recovery
results, may berecovery
the highest improved for by adding an
spodumene activator.
flotation Common
is still less than activators
70% for for
(Figure 2). The flotation recovery may be improved by adding an activator. Common activators
spodumene
(Figure 2). The flotation
flotation are metallic
recovery may ions
be (e.g.,
improved Fe 3+
by or Ca
adding 2+an
) [14]. Figure
activator. 5
Common shows that
activators by
foractivating
spodumene flotation are metallic ions (e.g., Fe3+ or Ca2+) [14]. Figure 5 shows that by activating
spodumene
spodumene
spodumeneflotation
usingusing are
calcium metallic
ions, the
calcium ions
ions, (e.g.,
recovery Fe
the recovery
3+ or Ca2+) [14]. Figure 5 shows that by activating
of spodumene
of spodumene is increased significantly
is increased to 90%.
significantly to In addition,
90%. In
spodumene
while using
the optimum
addition, calcium
while recoveryions,was
the optimum therecovery
recoverywas
initially of initially
spodumene
obtained is increased
atobtained
approximately significantlypH to
pH 10 (Figure
at approximately 10 90%.
2), byInactivating
(Figure 2), by
addition,
spodumene whileusing
activating the optimum
calcium using
spodumene recovery
ions the was ions
initially
recovery
calcium peak
the obtained at approximately
shifts towards
recovery peak shifts towardspH
a neutral pH. 10This
(Figure
a neutral 2),
makes
pH. Thisby
the process
makes
activating
the spodumene
process easierusing
to calcium
control ions
in the recovery
industrial peak
practice. shifts
In towards
addition, a
the neutral
pH pH.
range This
for themakes
maximum
easier to control in industrial practice. In addition, the pH range for the maximum flotation spodumene
the process easier to control
flotation in industrial practice. In addition, the pH range 8)formatches
the maximum
recovery after spodumene recovery
activation (i.e., pH ofafter activation
approximately (i.e.,
8) pH of approximately
matches well with the values reported well withby the
other
flotation spodumene
values reported recovery
by other after activation
researchers (i.e.,
[10,11]. pH of approximately 8) matches well with the
researchers
values reported[10,11].
by other researchers [10,11].

80-150 μm 40-80 μm
80-150 μm 40-80 μm
100
100 90
90 80
80 70
Recovery %

70 60
Recovery %

60 50
50 40
40 30
30 20
20 10
10 0
0 0 2 4 6 8 10 12
0 2 4 6 pH 8 10 12
pH
Figure 5.Figure 5. Theof
The effect effect of calcium
calcium activation
activation on on
thethe coarseand
coarse and fine fractions
fractions(NaOl: 250250
(NaOl: mg/L, CaClCaCl
mg/L, 2: 120 2
mg/L).
: 120 mg/L).
Figure 5. The effect of calcium activation on the coarse and fine fractions (NaOl: 250 mg/L, CaCl2: 120 mg/L).
The i.e.p.
The i.e.p. of spodumene
of spodumene is at
is at approximately pH
approximately pH 2, as discussed,
discussed,and anditsits
surface is negatively
surface is negatively
The i.e.p. at
of pH
spodumene isthe
at addition
approximately pH 2, as discussed, and its ofsurface is negatively
charged at pH > 2. After the addition of calcium ions, the zeta potential of the spodumene
charged > 2. After of calcium ions, the zeta potential the spodumene particles
particles
charged at pH >less
becomes 2. After the addition
negative (Figure of
6),calcium ions,the
indicating theadsorption
zeta potential
of of 2+the
Ca 2+onspodumene
the negativeparticles
sites of the
becomes less negative (Figure 6), indicating the adsorption of Ca
becomes less negative (Figure 6), indicating the adsorption of Ca on the negative sites of the
2+ on the negative sites of the
spodumene surface due to electrostatic attraction. As stated, when the collector (i.e., NaOl) is added,
the zeta potential of spodumene becomes more negative over a wide pH range. The ion-molecule
complexes react with the exposed Al sites, reducing the positive charge on the spodumene surface,
and therefore shifting the zeta potential to less negative values. Adding Ca2+ activator followed
 Minerals 2019, 9, x FOR PEER REVIEW 6 of 12

spodumene surface due to electrostatic attraction. As stated, when the collector (i.e., NaOl) is added,
Minerals zeta9, potential
the2019, 372 of spodumene becomes more negative over a wide pH range. The ion-molecule6 of 11
complexes react with the exposed Al sites, reducing the positive charge on the spodumene surface,
and therefore shifting the zeta potential to less negative values. Adding Ca2+ activator followed by
by NaOl
NaOldecreases
decreases the
the quantity
quantity ofof negative
negativecharge
chargeonon thethe surface
surface andand results
results in ainreduction
a reductionin thein the
electrostatic repulsion between the collector and Al sites and an increase in the interaction
electrostatic repulsion between the collector and Al sites and an increase in the interaction efficiency, efficiency,
whichwhich
can improve the the
can improve flotation of of
flotation spodumene.
spodumene.Ca Ca2+ adsorbson
2+ adsorbs onthe
thenegative
negative SiOSiO − site
– site of silica
of the the silica
tetrahedrons,
tetrahedrons, and and
thusthus increases
increases thethe densityofofavailable
density available adsorption
adsorption sites.
sites.Moreover,
Moreover, Ca2+ 2+ adsorb
Cacan can adsorb
on theonother
the other planes
planes of spodumene,
of spodumene, allowingfor
allowing fordenser
denser adsorption
adsorptionlayerlayerformation.
formation.

Spodumene Spodumene + Ca(II)

Spodumene + Ca(II) + NaOL

20

0
Zeta potential (mv)

0 2 4 6 8 10 12
-20

-40

-60

-80

-100
pH

Figure 6. Comparison of the zeta potential of the spodumene surface with or without NaOl and CaCl2
Figure 6. Comparison of the zeta potential of the spodumene surface with or without NaOl and CaCl2
(250 and
(250120
andmg/L, respectively).
120 mg/L, respectively).

It is evident thatthat
It is evident thethe
pulp pulppHpH plays
playsa averyveryimportant
important roleroleininspodumene
spodumene flotation.
flotation. The The
mainmain
regulators usedused
regulators in spodumene
in spodumeneflotation
flotation are generallyNaOH
are generally NaOH andand
Na2NaCO23.CO 3 . A comparison
A comparison betweenbetween
the
the effects
effectsofofthese
thesetwo
two pHpH regulators
regulators isisshown
shownininFigureFigure
7. 7. It can
It can be be seen
seen thatthat
NaOH NaOH results
results in much
in much
higher spodumene
higher spodumene recovery
recovery (than
(thanNaNa
2 CO
2CO 3 3)) when usedtotocontrol
when used controlthethe
pHpH , with
, with or without
or without activation.
activation.
This suggests that NaOH is a more suitable pH regulator in spodumene flotation.
This suggests that NaOH is a more suitable pH regulator in spodumene flotation. Figure 7 also shows Figure 7 also shows
that when
that when Na2 CONa2CO 3 is used as a pH regulator, the flotation recovery of the activated spodumene
3 is used as a pH regulator, the flotation recovery of the activated spodumene
decreases as the pH
decreases as the pH increases increases
fromfrom8 to811.
to 11. Meanwhile,
Meanwhile, thethe recovery
recovery ofofnon-activated
non-activatedspodumene
spodumene also
also drops when the pH increases. This is not the case when NaOH is used, indicating that an
drops when the pH increases. This is not the case when NaOH is used, indicating that an increased
increased dosage of Na2CO3 has a negative effect on spodumene recovery (dropping from 50% to 20%).
dosage of Na2 CO3 has a negative effect on spodumene recovery (dropping from 50% to 20%). On the
On the other hand, activated spodumene has a much higher recovery than the non-activated sample
otherwhen
hand,either
activated
NaOHspodumene
or Na2CO3 is used.has aThis
much higher
suggests recovery
that CaCl2 has than the non-activated
an activating sample when
effect on spodumene
eitherinNaOH or Na CO is used. This suggests that CaCl has
flotation, even if a depressant (i.e., Na2CO3 in the current case) is present.
2 3 2 an activating effect on spodumene in
Minerals 2019,
flotation, 9, x FOR
even PEER REVIEW
if a depressant (i.e., Na2 CO3 in the current case) is present. 7 of 12

100
90
80
70
Recovery %

60
50
40
30
20
10
0
7 8 9 10 11 12
pH
Figure 7. The influence of pH regulators (: NaOH, : Na2 CO3 ) on spodumene flotation recovery.
The results
Figure 7. Thefor the activated
influence and non-activated
of pH regulators (■: NaOH,spodumene
●: Na2CO3) are representedflotation
on spodumene by solidrecovery.
and dashed
The
lines, respectively.
results for the activated and non-activated spodumene are represented by solid and dashed lines,
respectively.

Many metallic ions are the effective components of flotation reagents (activators or depressants).
The hydration equilibrium of inorganic ions is the basis for studying flotation. Metal ions in the
hydrolysis reaction occurring in solution generate a variety of complexes. The concentration of each
Minerals 2019, 9, 372 7 of 11

Many metallic ions are the effective components of flotation reagents (activators or depressants).
The hydration equilibrium of inorganic ions is the basis for studying flotation. Metal ions in the
hydrolysis reaction occurring in solution generate a variety of complexes. The concentration of each
component can be obtained according to the solution equilibria:

[CaOH + ]
Ca2+ + OH− CaOH + β1 = = 101.4
[Ca2+ ][OH− ]

[Ca(OH )2(aq) ]
Ca2+ + 2OH− Ca(OH )2(aqueous) β2 = = 102.77
[Ca2+ ][OH− ]2
h i h i
CT = Ca2+ + Ca2+ + [Ca(OH )2(aqueous) ]
2
h i  
Ca2+ = CT / 1 + β1 [OH− ] + β2 [OH− ]
h i h i
CaOH + = β1 Ca2+ [OH− ]
2
h i
[Ca(OH )2(aqueous) ] = β2 Ca2+ [OH− ]
The solubility of Ca(OH)2 is 3.55 mmol/L and the initial concentration of CaCl2 was 1.08 mmol/L.
Therefore, there is no precipitation of Ca(OH)2 over the entire pH range. Chemical analysis of the
flotation solution revealed that when CaCl2 is added to the slurry, it is mainly in the form of Ca2+ at
pH < 12.5. The concentration of Ca(OH)+ increases with the pH and at pH > 12.5, Ca(OH)2(aqueous)
gradually dominates. Therefore, over the pH range of the flotation when the maximum spodumene
recovery was obtained, the calcium was predominantly in the form of Ca2+ ions.
A typical structure of spodumene is shown in Figure 8. Spodumene is composed of a series of
single-chain silica tetrahedrons along the y-axis which are bonded together by sharing an oxygen
between two neighboring tetrahedrons [6].
Minerals 2019, 9, x FOR PEER REVIEW 8 of 12

Figure
Figure 8. 8.The
Thecrystallographic
crystallographic structure
structureofofspodumene.
spodumene.

In flotation,
In flotation, the adsorption
the adsorption of collector
of the the collector is mainly
is mainly determined
determined by generation
by the the generation of new
of new surfaces
surfaces during grinding. For spodumene, the liberated surfaces
during grinding. For spodumene, the liberated surfaces mainly consist of broken Si–O andmainly consist of broken Si–O andAl–O
Al–O bonds. The lengths of these three bonds vary; the Li–O bond is the longest followed by Al–O
bonds. The lengths of these three bonds vary; the Li–O bond is the longest followed by Al–O and
and Si–O [15]. However, the strength of the Li–O bond is not high enough to form a bond, as shown
Si–O [15]. However, the strength of the Li–O bond is not high enough to form a bond, as shown in
in Figure 8. The Al–O bonds are longer than the Si–O bonds, so it is easier to break these bonds and
Figure 8. The
expose Al–O
more Al bonds are longer
ions, which causes than the Si–O bonds,
the adsorption of NaOl.soThis it isinteraction
easier to break
occursthese
over abonds
long and
expose more Al ions, which causes
distance compared to covalent bonding. the adsorption of NaOl. This interaction occurs over a long distance
comparedThe to covalent bonding.
total broken bond strengths per unit cell area were calculated as 9.372 × 10 , 6.352 × 1018, 18

The
4.734total
× 1018broken
and 7.524bond× 10strengths
18 valence/m per unit
2 for thecell area
{100}, were
{010}, calculated
{110} and {001}as × 1018 , 6.352
9.372respectively.
planes, × 1018 ,
The
4.734{110} 18
× 10plane andis 7.524
the weakest 18
× 10 crystalline
valence/m 2
plane,
for indicating
the {100},that cleavage
{010}, {110} occurs alongplanes,
and {001} the {110} plane
respectively.
during
The {110} the comminution
plane is the weakest process. Each plane,
crystalline crystalline plane has
indicating thata cleavage
distinct type and along
occurs number theof{110}
Al–Oplane
during the comminution process. Each crystalline plane has a distinct type and number unit
bonds, which leads to variance in the total bond strength. In terms of density of Al sites in the of Al–O
cell area, the crystalline planes are ranked in the order of {001} > {110} > {100} > {010}. The Al sites on
bonds, which leads to variance in the total bond strength. In terms of density of Al sites in the unit
the surfaces provide a high affinity for oleate molecules through complexation and the broken Al–O
bonds are responsible for adsorbing the oleic acid ions [16]. The {110} plane is still more favorable to
chemisorption with oleate than the {001} plane because it has two broken Al–O bonds which provide
two unsatisfied coordinates, whereas only one exists in the {001} plane. Therefore, the chemical
properties of the surface, such as the surface potential and hydrophobicity, are dominated by the
{110} crystalline planes. Recently, Zhu et al. [8] also reported that the adsorption of sodium oleate on
Minerals 2019, 9, 372 8 of 11

cell area, the crystalline planes are ranked in the order of {001} > {110} > {100} > {010}. The Al sites on
the surfaces provide a high affinity for oleate molecules through complexation and the broken Al–O
bonds are responsible for adsorbing the oleic acid ions [16]. The {110} plane is still more favorable to
chemisorption with oleate than the {001} plane because it has two broken Al–O bonds which provide
two unsatisfied coordinates, whereas only one exists in the {001} plane. Therefore, the chemical
properties of the surface, such as the surface potential and hydrophobicity, are dominated by the {110}
crystalline planes. Recently, Zhu et al. [8] also reported that the adsorption of sodium oleate on the
spodumene mineral occurs at the {100} and {110} surfaces.
The XRD patterns of the spodumene samples are shown in Figure 9. The relative intensities of the
four crystalline planes ({100}, {010}, {110} and {001}) are listed in Table 1. It should be noted that the
relative intensities only represent the relative amounts of phases in one sample. Therefore, a conversion
should be developed in order to compare the same phase between different samples. The ratio of the
amount of desired crystalline planes ({110}) to the amount of the three undesired crystalline planes
({100}, {010} and {001}) defines the relative quantity of desired planes in each fraction. Higher values
of this ratio indicate the presence of more {110} planes, more exposed Al sites and more collectors
adsorbed on the surface (in the current case, this ratio is higher for the 40–80 µm fraction than the
Minerals 2019, 9, x FOR PEER REVIEW 9 of 12
80–150 µm fraction). This indicates that the 40–80 µm fraction is preferable for collector adsorption.

Figure
Figure 9. The
9. The XRDXRD patterns
patterns of theofspodumene
the spodumene samples.
samples.

Table 1. Relative intensities of the main planes of the fine and coarse fractions of spodumene.
Table 1. Relative intensities of the main planes of the fine and coarse fractions of spodumene.
Crystalline Planes (h,k,l) 40–80 40–80 µm
80–150 80–150 µm
Crystalline Planes (h,k,l)
{110} (−1,−1,0) µm 56.9µm 72.1
{110} (−1,−1,0) 56.9 72.1
{110} {110} (−2,−2,0)
(−2,−2,0) 9.3 9.36.6 6.6
{110} {110} (−3,−3,0)
(−3,−3,0) 7.9 7.94.4 4.4
{100} (−2,0,0) 44.4 21.3
{100} (−2,0,0) 44.4 21.3
{100} (−4,0,0) 6.4 4.7
{100} {010} (−4,0,0)
(0,−2,0) 33.7 6.478.3 4.7
{010} {001} (0,0,−2)
(0,−2,0) 8.5 33.74.1 78.3
The ratio of {110} to {100} + {001} +
{001} {001} (0,0,−2) 0.80 8.50.76 4.1
Figure
The10ratio
shows that to
of {110} {110} is +the
{100} + {001}
main
{001} cleavage plane of spodumene. A total of one0.76
0.80 hundred
{110} planes were randomly selected in the images and their aspect ratios were calculated using
ImageJ software. The histograms of the aspect ratios presented in Figure 11 show that the {110} planes
Figure 10 shows that {110} is the main cleavage plane of spodumene. A total of one hundred {110}
from the 40–80 μm fraction exhibit a smaller aspect ratio than those in the coarse fraction. This is in
planes werewith
agreement randomly selected
the results in the
reported byimages
Xu et al.and[10],
their
whoaspect ratiosawere
proposed calculated
grinding methodusing
for ImageJ
software.
spodumene The histograms
that of the aspect
results in various particleratios
sizes.presented
Spodumene inisFigure
a very 11 show that
anisotropic the {110}
mineral. Dueplanes
to the from the
40–80 µm fraction
high tendency exhibit a smaller
of spodumene aspect
to generate ratio than
a cleavage those
plane, thein the coarse
monoclinic fraction.
structure This isofinthe
consists agreement
{110} planes as the side plane and the {001} planes as the basal plane [6]. When the
with the results reported by Xu et al. [10], who proposed a grinding method for spodumene that particles are slightly
crushed, the {110} planes are the most likely to break, so the quantity as well as the relative surface
area of the {110} planes increase more quickly than those of the {001} planes. The quantity of {001}
planes starts to increase as the particle size decreases (Table 1). The higher {001} planes adsorb less
NaOl, which could be responsible for the decreased floatability of the coarser fraction (Figure 2). It
should be noted that the very fine fraction (less than 40 μm) was not considered in this work due to
the complexity which may arise due to entrainment.
Minerals 2019, 9, 372 9 of 11

results in various particle sizes. Spodumene is a very anisotropic mineral. Due to the high tendency
of spodumene to generate a cleavage plane, the monoclinic structure consists of the {110} planes as
the side plane and the {001} planes as the basal plane [6]. When the particles are slightly crushed,
the {110} planes are the most likely to break, so the quantity as well as the relative surface area of the
{110} planes increase more quickly than those of the {001} planes. The quantity of {001} planes starts to
increase as the particle size decreases (Table 1). The higher {001} planes adsorb less NaOl, which could
be responsible for the decreased floatability of the coarser fraction (Figure 2). It should be noted that
the very fine fraction (less than 40 µm) was not considered in this work due to the complexity which
may arise due to entrainment.
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9, xPEER REVIEW
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Figure 10. Representative SEM images for the 80–150 μm (top) and 40-80 μm (bottom) fractions (The
scale of the top and bottom images are 600 and 200 μm, respectively).
Figure
Figure 10.10.Representative
Representative SEM
SEMimages
imagesfor the
for 80–150 μm (top)
the 80–150 µmand 40-80
(top) andμm40–80
(bottom)
µmfractions
(bottom)(The
fractions
scale of the top and bottom images are 600 and 200 μm, respectively).
(The scale of the top and bottom images are 600 and 200 µm, respectively).

30

30 25

25 20
Frequency

15
20
Frequency

10
15
5
10
0
5 0.0 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 7.0 7.5 8.0

0 Aspect ratio
0.0 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 7.0 7.5 8.0
Figure 11. Distribution of the aspect ratios for the {110} planes in the 40–80 µm (grey) and 80–150 µm
Figure 11. Distribution of the aspect ratios for the {110}
Aspect planes in the 40–80 μm (grey) and 80–150 μm
ratio
(black) fractions.
(black) fractions.

Figure 11. Distribution of the aspect ratios for the {110} planes in the 40–80 μm (grey) and 80–150 μm
4. Conclusions
(black) fractions.

4. Conclusions
Minerals 2019, 9, 372 10 of 11

4. Conclusions
The optimum pH for spodumene flotation was found to be approximately 10, and the optimum
dosage of sodium oleate was found to be 250 mg/L. After the addition of CaCl2 , spodumene flotation
recovery increased considerably to 90%. The effects of pH regulators were also investigated and it
was found that spodumene had poor floatability when Na2 CO3 was used as a pH regulator compared
to NaOH.
The i.e.p. of spodumene shifted to a lower pH when NaOl was added, which confirmed the
adsorption of oleate to the mineral surface. Activating spodumene with calcium ions makes the
mineral surface charge less negative due to the adsorption of Ca2+ on the surface.
To understand the flotation mechanism of spodumene, its crystallographic properties were
analyzed. The adsorption of NaOl was attributed to the chemisorption of oleate to the exposed Al
and Si sites, which were generated after breaking the Al–O and Si–O bonds on the mineral surface.
Through the calculation of the strength of the broken bonds on the spodumene surface, it was found
that the {110} planes are the most favorable for the adsorption of oleate. The {110} plane is the weakest
plane and spodumene has the highest tendency to cleave along the {110} plane. The XRD patterns of
spodumene revealed that the 40–80 µm fraction has more {001} planes than the 80–150 µm fraction,
which may explain why the former has better floatability.
The results obtained in this work suggest that the comminution process (e.g., crushing and
grinding) can affect the floatability of spodumene by changing its crystallography. Therefore, further
investigations into more suitable grinding methods which could increase the floatability of spodumene
are required.

Author Contributions: Methodology, L.F., L.L.; project administration, L.F., S.F.; investigation, L.L., I.F.,
supervision, L.F., I.F.; validation, L.F., I.F., S.F.; formal analysis, L.L., I.F.; original draft preparation, L.L;
writing—review and editing, S.F., L.F.; funding acquisition, L.F.
Funding: This research was funded by Labex Ressources21 (Investissements d’Avenir grant agreement no.
ANR-10-LABX-21).
Acknowledgments: Financial support from Labex Ressources21 (ANR, n◦ ANR-10-LABX-21 “Strategic Metals in
the 21st Century”) is acknowledged.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Statista, Total Global Consumption of Lithium from 2008 to 2016. Available online: https://www.statista.com
(accessed on 1 March 2019).
2. Rongguo, C.; Juan, G.; Liwen, Y.; Huy, D.; Liedtke, M. Supply and Demand of Lithium and Gallium; BGR, Federal
Institute for Geosciences and Natural Resources: Hannover, Germany, 2016.
3. Bulatovic, S.M. Beneficiation of Lithium Ores. In Handbook of Flotation Reagents: Chemistry, Theory and Practice,
Volume3: Flotation of Industrial Minerals; Elsevier: Amsterdam, The Netherlands, 2015; pp. 41–56.
4. Tian, J.; Xu, L.; Wu, H.; Fang, S.; Deng, W.; Peng, T.; Sun, W.; Hu, Y. A novel approach for flotation recovery
of spodumene, mica and feldspar from a lithium pegmatite ore. J. Clean. Prod. 2018, 174, 625–633. [CrossRef]
5. Wu, H.; Tian, J.; Xu, L.; Fang, S.; Zhang, Z.; Chi, R. Flotation and adsorption of a new mixed anionic/cationic
collector in the spodumene-feldspar system. Miner. Eng. 2018, 127, 42–47. [CrossRef]
6. Moon, K.S.; Fuerstenau, D.W. Surface crystal chemistry in selective flotation of spodumene (LiAl[SiO3 ]2 )
from other aluminosilicates. Int. J. Miner. Process. 2003, 72, 11–24. [CrossRef]
7. Kuntzinger, S.; Ghermani, N.E. Electron density distribution and Madelung potential in α-spodumene,
LiAl(SiO3 )2 , from two-wavelength high-resolution X-ray diffraction data. Acta Crystallogr. B 1999, 55,
273–284. [CrossRef] [PubMed]
8. Zhu, G.; Wang, X.; Li, E.; Wang, Y.; Miller, J.D. Wetting characterisations of spodumene surfaces as influenced
by collector. Miner. Eng. 2019, 130, 117–128. [CrossRef]
9. Liu, W.; Zhang, S.; Wang, W.; Zhang, J.; Yan, W.; Deng, J.; Feng, Q. The effects of Ca (II) and Mg (II) ions on
the flotation of spodumene using NaOl. Miner. Eng. 2015, 79, 40–46.
Minerals 2019, 9, 372 11 of 11

10. Xu, L.; Hu, Y.; Wu, H.; Tian, J.; Liu, J.; Gao, Z.; Wang, L. Surface crystal chemistry of spodumene with different
size fractions and implications for flotation. Sep. Purif. Technol. 2016, 169, 33–42. [CrossRef]
11. Yu, F.; Wang, Y.; Zhang, L.; Zhu, G. Role of oleic acid ionic À molecular complexes in the flotation of
spodumene. Miner. Eng. 2015, 71, 7–12. [CrossRef]
12. Amarante, M.M.; Sousa, A.B.; Leite, M.M. Processing a spodumene ore to obtain lithium concentrates for
addition to glass and ceramic bodies. Miner. Eng. 1999, 12, 433–436. [CrossRef]
13. Xu, L.; Peng, T.; Tian, J.; Hu, Z.; Lu, Y.; Sun, W. Anisotropic surface physicochemical properties of spodumene
and albite crystals: Implications for flotation separation. Appl. Surf. Sci. 2017, 425, 1005–1022. [CrossRef]
14. Wang, Y.; Yu, F. Effects of metallic ions on the flotation of spodumene and beryl. J. China Univ. Min. Technol.
2007, 17, 35–39. [CrossRef]
15. Arlt, T.; Angel, R.J. Displacive phase transitions in C-centred clinopyroxenes. Phys. Chem. Miner. 2000, 27,
719–731. [CrossRef]
16. Zhu, G.; Wang, Y.; Liu, X.; Yu, F.; Lu, D. The cleavage and surface properties of wet and dry ground
spodumene and their flotation behavior. Appl. Surf. Sci. 2015, 357, 333–339. [CrossRef]

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