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Article history:
Received 14 March 2012
Accepted 9 July 2012
Available online 4 October 2012
Keywords:
Oil agglomerate otation (OAF)
Molybdenite
Waste tailings
Recovery
a b s t r a c t
Neutral oils like kerosene, diesel, transformer and rapeseed oil were used as collectors or bridging
reagents in conventional otation and oil agglomeration otation (OAF) process, and a promising OAF
process has been developed for the recycling of ultrane molybdenite resources from the waste tailings.
p
a
The average size of collected particles (d50 ), agglomerates (d50 ) and their distribution of the froth concentrate were determined by laser particle size analyzer or sieve analysis. Conventional otation froth cannot catch the ultrane particles, so it is an ineffective process to recover molybdenum metal in the waste
tailings, while OAF has some advantages to recover ne minerals. And the best result was obtained from
transformer oil due to its appropriate length of carbon chain, kinematic viscosity and cyclical structure.
The oil amount plays a very important role on average size of the particles, with the increase of transa
p
former oil from 2.0 to 13.8 kg/t, d50 increases from 0.15 to 0.68 mm and d50 decreases from 9.06 to
a
p
2.05 lm. This nding suggests the bigger the d50 , the smaller the d50 , and the higher the recovery of
molybdenite.
The appropriate conditions for recovering ultrane molybdenite were determined as follows: dosage of
frother: 0.5 kg/t, natural pH: 6.2, stirring time: 3 min, and stirring intensity:400600 r/min. Lastly, the
closed cycle test and industrial application in the producing scale of 500 t/d were carried out, and result
shows 95% molybdenum was recovered with a satised grade of 22.62%.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
During conventional molybdenite otation practice, regrinding
and multi-stage cleaner are adopted to obtain satisfactory grade
and good recovery in molybdenum concentrate. However, because
greater size reduction is necessary to liberate the minerals, ne and
ultrane rougher or cleaner tailings are inevitably generated in the
process (Ansari and Pawlik, 2007; Rubio et al., 2007; Triffett et al.,
2008), and these tailings would cause numerous problems in concentration stage and other treatment stages. Since the conventional beneciation techniques like froth otation and gravity
concentration processes are inefcient in the ultrane size range
(Sivamohan, 1990; Snmez and Cebeci, 2003a; Miettinen et al.,
2010), a signicant amount of molybdenum is inevitably lost in
waste tailings and discharged to tailings pond. Therefore, the treatment of waste tailings by otation is an important subject of interest to researchers and engineers. This could potentially conserve
the mineral resources and reduce environmental waste.
The reuses of waste tailings are investigated in many countries,
which have a signicant advantage in terms of increasing metal
productivity and reducing the amount of waste to be rejected
Corresponding author. Tel./fax: +86 731 88879616.
E-mail address: huiwang1968@163.com (W. Hui).
0892-6875/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.mineng.2012.07.006
134
Mo
Cu
Zn
Ni
Pb
Content (%)
1.04
0.14
0.61
0.05
0.56
0.92
0.06
Na2O
0.35
Components
K2O
MgO
CaO
Al2O3
Fe2O3
MnO
TiO2
SiO2
Content (%)
0.23
2.57
24.14
5.13
18.98
1.82
0.46
42.86
Table 2
Particle size analysis and molybdenum distribution in the tailings.
Size fraction (mm)
Yield (%)
Grade of Mo (%)
Distribution of Mo (%)
+0.28
0.28 + 0.125
0.125 + 0.076
0.076 + 0.045
0.045 + 0.038
0.038
Total
2.11
7.69
8.17
10.32
3.66
68.06
100.00
0.13
0.19
0.22
0.36
0.68
1.39
1.04
0.26
1.40
1.72
3.56
2.39
90.67
100.00
135
Density (kg/m3, 20 C)
Fundamental ingredients
Kerosene
Diesel
Transformer oil
Rapeseed oil
800
840
895
915
1.6
3.7
11.5
13.3
24.0
27.2
29.5
27.3
C12C15
C15C18
C16C23
C16C22
n-Alkanes
n-Alkanes
Cycloalkanes
Unsaturated fatty acid
We have found that the molybdenite tailings can be agglomerated successfully with any of the oil used in this study. Unfortunately, the increase of vegetable oil (rapeseed oil) only has little
effect on molybdenum recovery, as presented in Fig. 2. The benet
of naphthenic vs linear chain oils can account for this phenomenon
(Smit and Bhasin, 1985). The fundamental ingredients of rapeseed
oil are unsaturated fatty acids, e.g. erucic acid, oleic acid and linoleic acid, and they are always used as the collectors of gangues,
especially for calcium, iron, aluminium, magnesium bearing minerals. When rapeseed oil is used as the bridging oil, the gangue particles tend to adsorb on the oil droplets, preventing their
coalescence. The surface of agglomerates are mostly occupied by
gangue minerals, which are the main components of the tailings;
while molybdenite particles mostly remain in the water phase
and do not attach to oil droplets, so they are not recovered.
Obviously, the other three oils can be successfully used in the
molybdenite OAF. The molybdenum recovery increases rapidly
with increasing the amount of bridging reagent from 2.0 to
136
Fig. 3. Particle size distribution of the raw tailings and froth concentrate.
Fig. 4. Product SEM images obtained in conventional and oil agglomeration otation.
6.9 kg/t and then it does not change reasonably at higher amounts.
On the other hand, too high concentration of bridging oil in the
solution would reduce the grade of nal concentrate. Considering
the recovery and grade relationship for molybdenite, the suitable
dosage of bridging oil was determined at 1214 kg/t (rst rougher
is 1012 kg/t and second rougher 2 kg/t).
In the agglomeration system, the length of carbon chain, kinematic viscosity and cycloalkane structure would make it easy to
form compact funicular aggregates, i.e. with larger amounts of
oil, funicular bridging occurs and more compact aggregates are
formed (Drzymala et al., 1986). The fundamental ingredient of kerosene and diesel is n-alkanes, but transformer oil is naphthenic
(Table 3). The transformer oil droplet can catch more ne molybdenite particles and shows the best recovery among the three oils. In
addition, it can be found that the average particle size of concentrate using transformer oil as bridging agent was the lowest
(Fig. 3e).
According to the concept of the critical surface tension of wetting, as developed by Zisman and co-workers, the solid or mineral
surface is completely wetted by the liquid if the surface tension of
liquid is equal to or less than the critical surface tension of the wet-
Fig. 5. Relationships among oil amount, d50 , d50 and otation recovery.
not be fully represented by the dry sieve analysis result, but the result should be consistent with statistical laws in the parallel test.
a
Accordingly, it can be conjectured the bigger the d50 , the smaller
p
the d50 , and the higher the molybdenum recovery. And it can be explained based on the surface area of small molybdenite particles,
which are wetted by the transformer oil, and make aggregates.
3.3. Operating conditions of oil agglomeration otation
There are many factors affecting the OAF process, and the major
ones are different oil types and dosages, frother dosages, pH, stirring time and intensity. These operating conditions were tested
as follows.
Transformer oil was used as bridging reagent with a dosage at
14 kg/t (rst-stage rougher 12 kg/t and second-stage rougher
2 kg/t), stirring speed is xed at 800 r/min and stirring time at
5 min. The effect of pine oil amount on OAF was carried out as
the owchart given in Fig. 1, and the results are shown in Fig. 6.
There are slight effects on the recovery of rougher concentrate
when the amount of pine oil increases from 0.30 to 0.75 kg/t, but
it plays an important role in the result, i.e. recovery and grade of
nal concentrate (Fig. 6). The concentrate recovery increases from
79.94% to 85.44% and then to 86.03% when the amount of pine oil
increases from 0.30 to 0.50 and then to 0.75 kg/t. At the same time,
the grade of the concentrate decreases from 38.21 to 35.84 and
then sharply to 16.34%. Hence, 0.5 kg/t pine oil is considered as
the proper amount for the otation separation process.
137
Pulp pH values can be adjusted from 6.2 to 10.3 by adding calcium oxide from 0 to 1.5 kg/t. The effect of pulp pH values on the
OAF is presented in Fig. 7. The gure shows that the recovery of
molybdenum is slightly affected by pH, whereas the grade shows
a downtrend and gradually decreases from 35.81% to 15.22% with
the pH increasing. During the test, it is found that the foaming ability and viscidity of pulp are improved with the increase of pH value
in alkaline solutions, which result in the increase of agglomerate
yield and gradual decrease of grade. Therefore, OAF can be carried
out at the pH near 6.2, which is the natural pH for tailing
suspensions.
At optional dosage, the effects of stirring time and agitation
intensity were studied in the OAF process, and the experimental
data are presented in Figs. 8 and 9, respectively.
For a short agglomeration time, the diameters of agglomerates
are smaller because of insufcient oil dispersion and the collisions
between particles. As the agglomeration time increased, larger
agglomerates were obtained due to an increase of particleparticle,
particlemicroagglomerate, and microagglomeratemicroagglomerate contact (Cebeci, 2003). With the increase of agglomerates
size, more and more ultrane molybdenites are collected to form
large agglomerates. To provide dispersion of oil as ne droplets
in the suspension, the oil agglomeration process requires higher
stirring speed. When particleparticle collision speed was increased by increasing the agitation intensity, agglomerates of a
much tighter structure were formed. However, a too higher stirring
speed, partial destruction of agglomerates happened by shear
forces and collisions of agglomerates to cell walls and to each other
(Snmez and Cebeci, 2003a). The experimental results indicate that
the desired particles can be selectively agglomerated and removed
from the slurry under appropriate physico-chemical conditions, i.e.
3 min stirring time with stirring intensity at 400600 r/min is sufcient for recovering molybdenite from ultrane waste tailings by
oil agglomerate otation.
4. Locked cycle test and industrial application of oil
agglomeration otation
A locked cycle OAF test, with the owsheet of one-stage rougher, one-stage scavenger, four-stage cleaner and middlings return to
the former cleaner, has been conducted to assess beneciation performance under simulated continuous operating condition. On this
basis, the industrial experiment producing 500 t/d molybdenite
was carried out at the spot of tailings reservoir. Results of laboratory locked cycle test and normal production indices are summarized in Table 4.
As seen from Table 4, in normal production processes of
agglomeration otation, 95% molybdenum is recovered into the
froth products (concentrate) with a molybdenum grade at
22.62%, and only 5% molybdenum still lost in secondary tailings.
138
Table 4
Results of locked cycle test and industrial application of oil agglomeration otation.
Items
Products
Laboratory locked
cycle test
Concentrates
Secondary
tailings
Original
tailings
Industrial application
Concentrates
Secondary
tailings
Original
tailings
Yield
(%)
3.05
96.95
100.00
4.39
95.61
100.00
Mo grade
(%)
Mo recovery
(%)
31.17
0.093
91
9
1.04
100
22.62
0.056
95
5
1.05
100
size. While the average particle size of OAF concentrate is less than
5.92 lm, and the products have ultrane compact layered molybdenite structure, so OAF has some advantages to recovering ne
minerals.
The molybdenite tailings can be successfully agglomerated with
kerosene, diesel, transformer oil or rapeseed oil, but rapeseed oil
shows little effect on increasing the recovery of molybdenum,
due to the fact that rapeseed oil is an unsaturated fatty acid, which
is also the gangue collector. When rapeseed oil is used as the bridging oil, most of the surface of agglomerates is occupied by undesired particles. The best result is obtained from transformer oil
because its length of carbon chain, kinematic viscosity and cycloalkane structure are all in favorable conditions. The average particle
size of agglomeration concentrate using transformer oil as bridging
oil is the lowest one, 2.05 lm.
The oils amount plays a very important role on the average size of
p
a
collected particles (d50 ), average size of agglomerates (d50 ) and otation recoveries. With the increase of transformer oil from 2.0 to
a
p
13.8 kg/t, d50 increases from 0.15 to 0.68 mm and d50 decreases from
a
9.06 to 2.05 lm. Accordingly, it can be conjectured the bigger the d50 ,
p
the smaller the d50 , and the higher the molybdenum recovery.
There are many factors affecting the OAF process, and the dosage of 0.5 kg/t frother, natural pH and stirring time of 3 min, stirring intensity of 400600 r/min are considered as the appropriate
conditions. Practice has proven that OAF process can be considered
as a remarkable improvement technology in recovery of ultrane
molybdenite from waste tailings. Lastly, the locked cycle test and
industrial experiment in the producing scale of 500 t/d have been
carried out, in normal production processes, 95% molybdenum is
recovered with a satised grade of 22.62%.
Acknowledgements
The authors acknowledge the Key Laboratory of Resources
Chemistry of Nonferrous Metals, Ministry of Education (Central
South University) for the laboratories and nancial support, and
we would like to express our sincere appreciation to the anonymous reviewers for their insightful comments, which have greatly
aided us in improving the quality of the paper.
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