Materials Transactions, Vol. 51, No. 7 (2010) pp.

1367 to 1369
#2010 The Japan Institute of Metals EXPRESS RAPID PUBLICATION

The Effect of Sodium Silicate as pH Modifier and Depressant

in the Froth Flotation of Molybdenite Ores
Chul-Hyun Park and Ho-Seok Jeon*
Korea Institute of Geoscience and Mineral Resources, Daejeon 305-350, Korea

In flotation of porphyry molybdenite ores or copper-molybdenite ores using oil collector, a molybdenite (MoS2 ) concentrate has mainly
been separated by combination of sodium silicate (Na2 SiO3 ) and lime (CaO) at about pH 9–11. In this research, the role of sodium silicate and
the effect of collector (kerosene) in flotation of Dong-won molybdenite ores from Korea have been observed. It was confirmed that sodium
silicate could adjust the pH of pulp to 11. Furthermore, flotation efficiency using sodium silicate was better more than that using lime in the
alkaline conditions (pH 9.5–11). It was demonstrated that sodium silicate could be used not only as pH modifier but also as depressant/dispersant
of slime. Also Mo grade of 54.1% and recovery of 92.5% were successfully obtained at 75 g/t kerosene and 1.25 kg/t Na2 SiO3 (pH 10).
[doi:10.2320/matertrans.M2009397]

(Received November 30, 2009; Accepted February 26, 2010; Published June 25, 2010)
Keywords: molybdenite, flotation, Na2 SiO3 , collector, depressant, potential of hydrogen (pH)

1. Introduction Q

G - Grossular
Korea imports molybdenum of about 3.3 thousand ton per Q - Quartz
year from abroad, owing to a development of steel manu- H - Hedenbergite
G M - Molybdenite
Intensity

factures.1) Hence the development of flotation technology for G

Dong-won molybdenite ores (the only mine) in Korea has

been demanded. Molybdenum is mainly used as an alloying
agent for superalloys, stainless steels, cast irons, refractories,
pigments, lubricants and others, due to its unique physical
and chemical properties.2,3)
The primary source of molybdenum is the mineral
molybdenite (MoS2 ) and it is contributed from porphyry
molybdenite and porphyry copper-molybdenite ores. The
molybdenite is hydrophobic, due to the perfect cleavage and
micaceous form of mineral, and then its natural floatability is
high more than other minerals.4,5) The broken (crushed or
ground) in sulphur-molybdenum bonds generates ‘‘edges’’
sites and van der Waals bonds ‘‘faces’’ sites. Thus the
‘‘edges’’ are highly polar but the ‘‘faces’’ are not and are
naturally hydrophobic. The quantity of polar areas ‘‘edges’’ is
smaller and non-polar ‘‘faces’’ represent the predominant part
when comminuted.5,6)
Thus the floatability of molybdenite is enhanced if an
insoluble, nonpolar hydrocarbon oil is added to flotation
cell.7) Collectors in molybdenite flotation have mainly been
used to a fuel oil and stove oil (kerosene) like hydrocarbon
compounds than xanthates to be used as collector of sulfide
minerals. Molybdenite and quartz particles are negatively
charged at the pH commonly.2,8) Calcium ions are found to
exhibit a strong affinity to adsorb onto surface of molybdenite
and quartz, and then calcium ions are able to reverse or to
reduce their zeta potential.2,4) Physicochemical investigations
regarding the role of depressants in molybdenite flotation are
very few. Sodium silicate has quite often been used to
disperse the slime layers formed on the mineral particles, and
as depressants of gangue minerals (quartz, clay minerals, etc.)
to be particularly detrimental to the molybdenite recovery.6,9)
This work aims at developing a reliable flotation technique
that can separate up to 52% Mo grade (MoS2 , 87%) with 90%
*Corresponding author, E-mail: hsjeon@kigam.re.kr
HG Q
G G
G
M
0 10° 20° 30° 40° 50° 60°
2θ
Fig. 1 XRD patterns of raw molybdenite ores using Cu K
target.
recovery from Dong-won molybdenite ores, based on the
control of the hydrophobic and hydrophilic of target mineral
and gangue minerals. Particularly, our study is focused on
estimating variables such as pH modifier and dosage of
collector that affect the molybdenite flotation.
2. Experimental
2.1 Materials and agents
Molybdenite ores used in this study were obtained from
a local plant (Dongwon, Co., Ltd.). Figure 1 shows XRD
pattern on raw sample using Cu K
target. Target mineral
was molybdenite (MoS2 ) and gangue minerals were silicate
minerals such as quartz (SiO2 ), hedenbergite (CaFe(SiO3 )2 ),
and grossular (Ca3 Al2 (SiO4 )3 ). Chemical analysis of raw
sample is reported in Table 1. The content of Mo was 0.35%
and calcium oxide (CaO) was 27%, and impurities such as
Pb, Zn, and Cu that can consist in sulfide minerals were
relatively low as 0.0005%, 0.042% and 0.022%, respectively.
Reagents used in flotation tests were sulfuric acid (H2 SO4 ),
and lime (CaO) or sodium silicate (Na2 SiO3
9H2 O, Junsei
chemical, Co. Ltd) for adjusting pH, and fuel oil (kerosene,
Junsei) as flotation collector.
1368 C.-H. Park and H.-S. Jeon

Table 1 Chemical analysis of raw molybdenite ores used in this study. 100

90
Metal elements (mass%)

Grade & Recovery of Mo (%)

80
Mo Pb Zn Fe Cu Re Mo recovery using H2SO4
Mo recovery at Natural pH 8.7
70 Mo recovery using CaO
0.35 <0:0005 0.042 8.64 0.022 — Mo recovery using Na2SiO3
Critical Mo grade: 59.9%
60
Chemical compositions (mass%)
50
SiO2 CaO Al2 O3 MgO MnO K2 O
40
46.07 27.00 2.91 1.41 1.64 0.59 Mo grade using H2SO4
30
Mo grade at Natural pH 8.7
Mo grade using CaO
20
Mo grade using Na2SiO3
Feed
Molybdenite ore. 10

0
Jaw crusher
3 4 5 6 7 8 9 10 11 12

Cone crusher pH
Pulverizer
Fig. 3 Effect of pH on grade and recovery of molybdenite in froth flotation.
Oversize Rod mill(-150 mesh) (20% (solids) pulp concentrate, 1.25 kg/t kerosene, 75 g/t AF65, pulp
Under size temp. of 20 C and cleaning of twice)
Kerosene, AF65,
Na 2SiO 3 or CaO Rougher flotation

Rougher conc. (MoS2 )
Cleaning flotation
Final conc.(MoS2 ) Middlings
Fig. 2 Flow sheet of froth flotation for recovery of molybdenite.
2.2 Method
Flotation machine used in this study was Denver sub-A
flotator of lab-scale. Figure 2 shows a flow sheet of froth
flotation for the recovery of molybdenite. The sample was
crushed and ground, and the minus 150 mesh fraction was
used for flotation tests, and then the sample were fed into
flotation cell and agitated in 20% (solids) pulp concentrate
for 5 min. Reagents in sequence of pH modifiers (CaO or
Na2 SiO3 ), depressant (Na2 SiO3 ), collector (kerosene) and
frother (Aeroforth 65) were added into pulp, and finally
molybdenite was floated with adsorbed onto bubbles. At
this time, a reaction time per reagent was 3 min and final
concentrate was obtained through rougher flotation of 1 time
and clean flotation of twice, and recovery time of concen-
trates was 10 min.
Grade and recovery were mainly used as standard for
estimating the separation efficiency and mass balance of
valuable mineral (or target material). Grade is the content
(%) of valuable mineral in raw ores, concentrate or tailing.
Recovery is the mass (%) of valuable mineral transferred
from raw ores to concentrate. Molecular weight ratio of Mo
and S2 is 59:9 : 40:1, and hence ‘‘critical’’ Mo grade is 59.9%
(a dotted line in graph). Mo grade is the content (mass%)
of Mo material in the concentrate, and its recovery eq. (1)
is in the following:
cC ð f  tÞc
Re ¼ ¼  100ð%Þ
fF ðc  tÞ f
Where, Re is the recovery of Mo in the concentrate separated
from feed (raw ores), and f : the content of target material in
the feed; c: the content of target material in the concentrate
(product fraction); t: the content of target material in the
tailing (reject fraction); F: mass of the feed; C: mass of
concentrate (product fraction); T: mass of the tailing (reject
fraction).
Tailing Analysis equipments used in this study are in the
following: X-ray diffractometer (Rigaku D-max-2500PC,
Rigaku/MSC, Inc., TX, U.S.A), the inductively coupled
plasma (ICP) method (JY-38 plus, Horiba Ltd, Kyoto, Japan),
a scanning electron microscope (JSM-6380LV, JEOL Ltd,
Japan) equipped with an energy dispersive X-ray spectrom-
eter (Link Isis 3.0, Oxford Instrument plc, U.K).
3. Results and Discussion
3.1 Effect of sodium silicate in alkali pH
The effect of pH on grade and recovery of molybdenite in
froth flotation is shown in Fig. 3. Experiments were per-
formed at 20% (solids) pulp concentrate, pulp temp. of 20 C,
1.25 kg/t kerosene, 75 g/t AF65, and cleaning of twice. The
natural pH of pulp was relatively high as 8.7. This is
attributed to limestone skarn minerals (calcic-hedenbergite,
grossular)10) as shown in Fig. 1 and Table 1. Mo recovery
curve decreased considerably as pH decreased toward acid
and Mo grade decreased gently. The molybdenite concentrate
was strongly agglomerated at pH 4 close to the isoelectric
point (pH 3)5) of molybdenite. The results showed that Mo
grade and recovery decreased with decreasing pH of pulp.
The reason may be, first: agglomeration between minerals
owing to a decrease of electrostatic repulsion between the
negatively charged gangue minerals (quartz) and molybden-
ite,2) second: a slime coating the surface of molybdenite.
Particularly, Hemlund11) affirmed that a slime coating pre-
vents the adsorption of collector onto the surface of molyb-
denite and then it deteriorates the floatability of molybdenite.
In the range of alkali (pH 9.5–11), lime and sodium silicate
were individually used as pH modifier. In case of lime, Mo
grade in pH 10 increased over 3% than that of natural pH,
ð1Þ whereas recovery continually decreased from pH 9.5 to 11.
This may be attributed to the interaction between minerals
and the introduced calcium ions in pulp. At high pH, calcium
ions form the calcium hydroxy complex Ca(OH)þ and then
heterocoagulation of molybdenite and quartz particles are
formed and their surface potential is decreased.2,7) It appears
that heterocoagulation of molybdenite and quartz particles in
pulp containing large amounts of lime impaired the float-
ability of molybdenite.
 The Effect of Sodium Silicate as pH Modifier and Depressant in the Froth Flotation of Molybdenite Ores
100
90
Grade & Recovery of Mo (%)
80
70
60
50
40
30
Mo grade using Na2SiO3 (1.25kg/t, pH 10)
20 Mo grade at Natural pH 8.7
10
0
0 25 50
Dosage of oil collector (kerosene, g /t)
Fig. 4 Effect of oil collector on grade and recovery of molybdenite in froth
flotation. (20% (solids) pulp concentrate, 75 g/t AF65, pulp temp. of 20 C
and cleaning of twice)
In case of sodium silicate, both Mo grade and recovery
increased as pH increased. The results indicate that the Mo
grade and recovery curves shift considerably, depending on
the pH. At pH 10, the maximum Mo grade and recovery were
54.1% and 92.5%, respectively. A stable dispersion of the
particles is important in flotation and sodium silicate has
been used habitually for a dispersant/depressant.
Na2 SiO3 þ 2H2 O
H2 SiO3 þ 2Naþ þ 2OH ð2Þ
 þ
H2 SiO3
HSiO3 þ H ð3Þ
HSiO3 
SiO3 2 þ Hþ
Form above chemical eq. (2), (3) and (4), three anionic
species are formed in pulp: OH , HSiO3  , and SiO3 2 .
The OH ion increases the pH of pulp, whereas HSiO3  and
SiO3 2 are the main depressing/dispersing species (miner-
als) of silicates.13,14) We consider that a stable dispersion of
the particles in pulp is attributed to repulsion between anionic
species and minerals. Especially, it can prevent a slime
coating onto the surface of molybdenite or minerals.15,16)
Thus it improves not only the adsorption of collector onto the
surface of molybdenite but also the floatability of molybden-
ite. From above results, it was demonstrated that sodium
silicate could be used not only as pH modifier but also as
depressant/dispersant of slime.
3.2 Effect of collector
The effect of collector on grade and recovery of molyb-
denite in froth flotation is shown in Fig. 4. Experiments were
performed at 20% (solids) pulp concentrate, pulp temp. of
20 C, 75 g/t AF65, and cleaning of twice. Mo recovery
curves increased considerably as dosage of kerosene increas-
ed, whereas Mo grade curves decreased gradually. The
separation efficiency of molybdenite was effective when the
dosage of kerosene was adjusted to 75 g/t. In comparison
to natural pH, separation efficiency of pH 10 was more
effective, due to a role of sodium silicate. The maximum Mo
grade and recovery were 54.1% and 92.5%, respectively.
As SEM & EDAX on final concentrate shown in Fig. 5, the
molybdenite showed well-developed cleavage and mica-
ceous form, and a small amount of SiO2 except molybdenite
presented in concentrate. It appears that high-grade molyb-
denite was successfully obtained from gangue minerals.
1369
Mo recovery using Na2SiO3(1.25kg/t, pH 10)
Mo recovery at Natural pH 8.7
Critical Mo grade: 59.9%
75 100 125
Fig. 5 SEM & EDAX on final concentrates (500).
4. Summary
The role of sodium silicate and the dosage of kerosene
which could affect molybdenite flotation have been observed.
From test results, it was confirmed that sodium silicate to
be used with depressant/dispersant could adjust the pH of
pulp to 11. Furthermore, flotation efficiency using sodium
silicate was better more than that using lime in the alkaline
conditions (pH 9.5–11). It was demonstrated that sodium
silicate could be used not only as pH modifier but also as
depressant/dispersant of slime. The separation efficiency
of molybdenite was effective when the dosage of kerosene
was adjusted to 75 g/t. A Mo grade of 54.1% and a recovery
ð4Þ of 92.5% were successfully obtained from gangue minerals
12,13)
at 75 g/t kerosene and 1.25 kg/t Na2 SiO3 (pH 10).
Acknowledgments
The authors would like to express special thanks to the
Korea Institute of Energy Technology Evaluation and
Planning, Energy/Resource R&D Program of the Ministry
of Knowledge Economy of Korea for financial support.
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