Optimizing the flotation of sulfide fines using emulsified oil extender
technique
J. Rubio, F. Capponi, R.T. Rodrigues, and E. Matiolo
Departamento de Engenharia de Minas-DEMIN. Laboratório de Tecnologia Mineral e Ambiental-
LTM. Universidade Federal do Rio Grande do Sul-UFRGS,
Av. Bento Gonçalves, 9500 - Prédio 75 - Sala 126, Bairro Agronomia, Porto Alegre - RS, Brazil;
jrubio@ufrgs.br; http://www.lapes.ufrgs.br/ltm
ABSTRACT
The treatment of a copper/molybdenum sulfide
ore (0.94 % Cu and 0.05% Mo) using emulsified
oil extender flotation (Ext-F) was studied at
laboratory scale. Results obtained were
compared with a “standardized” mill laboratory
procedure, measuring concentrate grade and
recovery (size by size results included), “true”
(bubbles-particles attachment only) flotation
recoveries and process kinetics. The Ext-F
technique yielded higher metallurgical
efficiencies, especially for the fines (<37 μm),
than the mill standard with emulsified Diesel oil
(> 60 gt-1). Concentrate recoveries with 60-90
gt-1 Diesel oil droplets (3-6 µm) and their
process kinetic values were always of the order
of 3-6 % higher, at similar concentrate grades,
either for copper or molybdenum sulfides. Size
by size flotation results proved that
metallurgical and kinetic gains can be attributed,
mainly, to fines (37-5 μm) and ultrafines (< 5
μm) enhancement (8-15% higher). Data
obtained are discussed in terms of chemical,
physical and physicochemical parameters
related to a better oil attachment and capture of
particles by bubbles. Thus, it is believed that the
emulsified oil droplets interact firstly with the
mineral surfaces, then spread out as oil lenses,
enhance hydrophobicity and allow aggregation
of the very fines. Theses stages do not occur
markedly when the oil does not interact properly
with the collector coated sulfides (low chemical
affinity) or when the oil was not emulsified. The
potential (advantages) of the Ext-F technique
for fine ore processing and the practical forms
for industrial oil emulsification are envisaged.
1. INTRODUCTION
The recovery, by flotation, of the fine (< 37 µm)
mineral particles is on of the major (and old)
technical challenges in the area of mineral
processing (Trahar, 1981, Sivamohan, 1990,
Collins and Read, 1971, Shibata and Fuerstenau,
2003, Rubio et al. 2003, 2006). In some cases,
certain mineral ores must be ground to very fine
particles because of the decrease in the grade
and the increase of complex ores.
Flotation plants have been historically
designed to recover mid-sized particles (Cu or
Mo) having good liberation and high flotation
rate constant, but the fine fractions! (Trahar,
1981, Rubio et al. 2003.
The alternatives for reducing the generation
of fines are possible by controlling and
optimizing crushing, grinding and re-grinding
stages, classification of the flotation feed into
fines and coarse circuits. More, Unit and/or
“Rougher-flash” operations because separate off
(from the conventional flotation circuit) a fairly
rich concentrate (as final product) reduce
substantially the mass to an eventual rougher
concentrate regrinding.
On the other hand, all existing models are
addressed to the need for a wide bubble size
distribution (100µm-2 mm) to obtain a better
size-by-size flotation (Yoon 2000, Franzidis and
Manlapig, 1999, Phan et al. 2003).
However, conventional cells do not provide
sufficient bubbles in the range < 600 µm.
Upcoming flotation devices, namely Jet
(Jameson) flotation cell and the “Microcel”
column claim that a substantial amount of
bubbles < 600 µm are generated and
consequently they should, in principle, be more
245
suitable for fines recovery (Mohanty and
Honaker, 1999, Jameson and Manlapig, 1991,
Yoon and Luttrell, 1994). Yet, the problem of
recovering the fines and specially the ultrafines
(<13 µm) by flotation still continues.
Aggregation of particles, with the use of
reagents (surfactants and oils), to solve the
problems of fineness has been attempted by
many ways (Kitchener, 1978, Song, et al. 1999,
Warren, 1992). Again, none of these techniques
appear to be used industrially.
Non-polar oils have been also used to
aggregate (agglomeration, in this case) fine
particles at varying oil /solids ratio. The higher
the oil concentration, the bigger are the
agglomerates being formed. These units may be
separated either using air bubbles or by gravity
2. EXPERIMENTAL
2.1 Materials
Ore. Copper porphyry samples, containing 0.94-
0.98 % Cu and 0.04-0.06 % Mo, were supplied
by Codelco-Chile. Yet, the emphasis, in this
work, was given to the copper sulfides as they
are the main (worthy) minerals in the company
ore. About 1/3 of the mass and about 37 % of
the total copper content is in the fines and
ultrafines fractions. Figure 1 show feed size-to-
size mass and copper distribution down to 5 μm
using micro sieves (Restch model USG).
Particles less than 5 μm were considered as
ultrafines (UF) in this work.
100 1

when agglomerate sizes are bigger (high oil 90

Weight, %
0,9

dosages). The latter is known as spherical 80 0,8

Copper, %
agglomeration (Mehrotra et al. 1983, 70 0,7

Laskowski, 1992). However, there is a situation, 60 0,6

Weight, %

Copper, %
not much explored, whereby the oil interact 50 0,5
firstly (as droplets) with the hydrophobic 40 0,4
mineral surfaces, then spreads it out as an oil 30 0,3
layer. This leads to an optimised flotation, 20 0,2
known as “extender” flotation, which appears to 10 0,1
combine an enhanced hydrophobicity with some
0 0
degree of particle aggregation (Laskowski and > 297 210 149 74 37 15 5 <5
Dai, 1993, Laskowski and Wang, 1997). Size, μm
More, oils may be added as coarse droplets Figure 1. Copper and mass size distribution in sample.
or as emulsified (micro-droplets) in
concentrations of the order of 20-100 g⋅t-1, 2.2 Reagents
together or after collector addition (Song et al.
1999, Duong et al. 2000; Laskowski, 1992, Common collectors and frothers mixtures for
Laskowski and Wang, 1997. Thus, the oil Cu and Mo sulphides were used. Lime, as pH
extender process begins with particle-oil regulator to pH 10.5 was added at the
droplets interactions (is not adsorption), then conditioning stage together with SF-113
there is a sort of molecular recognition (sodium isopropyl xanthate) at 30 gt-1
(hydrophobic effect) which leads to lenses concentrations. The frother (20 gt-1) was a
formation, spreading and finally aggregation. mixture of DF - 250 (a propylene glycol), MIBC
The word extender refers to the spreading stage (methyl isobutyl carbinol) and pine oil. Diesel,
of the oil lenses Kerosene, vegetal oil (corn oil) and 25W40
The aim of this work is to compare, at engine motor oil (Esso) were the oils studied
laboratory scale, standardized flotation tests and corresponded to commercial chemicals.
with oil extender flotation using emulsified oils Diesel oil has a density of 0.83 gcm-3, a 38.8
(various kinds). Comparisons were measured API grade and a viscosity of 4.5 cp (mPa.s);
through the separation parameters: grade, kerosene: 0.79 gcm-3 density, 46.80 API grade
recovery (global and true flotation) and rate and 1.8 mPa⋅s, the viscosity.
constants included size-by-size results to assess
the flotation behavior of the fine fractions (Cu 2.3 Methods
and Mo). Conventional, "standardized" (mill) kinetic
flotation tests were conducted in a 3L laboratory

246
Denver D12 cell. Conditioning of the feed (38
% solids content, pH 10.5), at 1000 rpm (no
turbulence), was performed in the same flotation
cell, during 3 min to allow collector and frother
adsorption. Data (quadruplicate) were obtained
from concentrates taken at 1, 3, 5, 7 and 9 min
flotation using a mechanical scrapper and
keeping constant the pulp volume. Samples
(concentrates and tailings) were then filtered,
dried, weighed and analyzed for copper and
molybdenum by atomic absorption.
The Rinf and k constants for the Klimpel
model (best model for the data obtained) were
obtained using a nonlinear regression method
(least square fitting). In all the fittings the R2
value was about 0.99. Mean STD Rinf Cu =
84.7 +/- 0.63; Mean STD Rinf Mo = 72.4 +/-
0.73.
Extender flotation tests. Here, oil-in-water
emulsions were prepared using a high free
rotational speed stirrer (Turrax) up to 23.000
rpm, during 10 min. Figure 2 shows the effect of
Diesel Oil (DO) concentration on droplet sizes.
The droplets size distributions (volumetric
percentage) were measured in laser diffraction
equipment (CILAS™ 1064). All analyses were
done in duplicate, at room temperature and at
the natural pH of the oil-in water emulsion. The
stock oil-in water emulsions remained stable
during the tests (coalescence was not observed).
The emulsions were mechanically stabilized
(emulsifier reagent or an encapsulation
technique was not used.
100
Cumulative percent passing, %
80
60
40
6 g/L 15 g/L
20 g/L 25 g/L
20
30 g/L
0 Figure 3: STD flotation of the Copper sulphide ore:
0 3 6 9 12
Droplets size, μm
Figure 2: Diesel oil droplet size distribution (oil-in- water
emulsions) as a function of oil concentration in water.
Figure 2 show that a D50 of about 3 μm was
obtained for the droplets, independently on oil
concentration. The “extender” oils were used as
an extra reagent added after the collector and
frother addition during the conventional
conditioning. Oil concentrations were 30, 60, 90
and 120 gt-1. Oils were added to water at the
desired pH 10.5, and the ratio was kept at 1:99.
After emulsification, the oil was added into the
aqueous phase and the flotation proceeded
similarly to the standard mill flotation test. All
concentrates were analyzed by the content of Cu
and Mo and the process efficiency was
measured by evaluating separation parameter
recovery, “true” recovery (Warren 1985), grade
and constant rate. Finally, to assess the
performance of flotation in the F and UF
fractions, size by size copper recoveries were
measured in the fractions: > 40 µm; 40-15 µm;
15-5 µm and < 5 µm.
3. RESULTS AND DISCUSSION
3.1 Standard flotation tests
Recovery-grade curves are presented in Figure 3
and 4 for both sulfides. Results show copper
recoveries (up to 9 min) of the order of 84-85 %
Cu. Mo recoveries reached almost 74 % with
rate constant (Klimpel model) of approximately
2.2 min-1 (Tab. 1). All results presented very
low standard deviation (< 1 %) with all data
reliable for process comparisons.
16
15
Cooper grade, %
STD-1
14
STD-2
STD-3
13
STD-4
STD-Average
12
50 60 70 80 90
Copper recovery, %
15 Grade-recovery curves.
247
 0,54 90 78,0

Molybdenum recovery, %
Molybdenum grade, %

Copper recovery, %
0,51 88 76,5

86 75,0
0,48

84 73,5
0,45 STD-1 STD-2
Copper Molybdenum
STD-3 STD-4
STD-Average
82 72,0
0,42 STD 30 60 90 120
-1
40 50 60 70 80 Diesel oil concentration, g.t
Molybdenum recovery, % Figure 5: Comparative sulfide flotation recoveries (9 min
Figure 4: STD flotation of a Molybdenite: Grade-recovery flotation) for Standard (STD) and Extender flotation, as a
curves. function of Diesel oil concentration.

3.2 Extender flotation studies 3,60 2,8

K Molybdenum, min-1 (Klimpel)

K Copper, min-1 (Klimpel)

Comparative results of emulsified extender

3,45 2,6
flotation of Cu-Mo sulfides (Table I) show that
naphtenic bearing oils such as Diesel oil and
Esso motor were more efficient than Kerosene 3,30 2,4
(a light oil). Thus separation parameters were
higher for these oils when compared to the mill 3,15 2,2
standard or kerosene oil-in-water emulsions,
especially kinetic and the true recoveries (3-6 % Copper Molybdenum
3,00 2,0
higher). The corn oil, emulsified or not,
STD 30 60 90 120
decreased significantly overall recoveries, -1
Diesel oil concentration, g.t
increased the froth viscosity and highly reduced
Figure 6: Comparative sulfide flotation kinetics values (9
the froth height. min flotation) for Standard (STD) and Extender flotation,
Flotation results, not shown here, with the as a function of Diesel oil concentration
non-emulsified oils, were unsatisfactory and
produced a significant froth height reduction 3.3 Size-by-size results and mechanisms
(depletion). This problem was minimal for involved
either emulsified DO or K, showing stable and
fluids froths. According to Hoover and Figures 7 and 8 show size-by-size copper and
Malhotra, 1976 and Laskowski, 1992, all their molybdenum recoveries for oil (DO, 90 gt-1),
results can be explained on the basis of oil compared to the mill standard. According to
attachment affinities for the sulfides expectations, these figures show clearly higher
Figures 5 and 6 show comparative results recoveries in practically all fractions, especially
between the mill standard test and with Diesel in the fine and ultrafines fractions (10-15 %
oil-in water emulsions. Best results were higher, for Cu or Mo). Results and the true
obtained, for both sulfides, with the “extender” recoveries support the hypothesis of the enhance
diesel oil (90 gt-1) and recoveries showed to bubbles-particles capture after oil droplets
decrease after this concentration, when attachment, spreading and aggregation. Should
aggregates began to grow and were too big to the F and UF were not floated, no “true”
float. flotation values higher than the mill flotation
standard would have been obtained.

248
Table I: Emulsified extender flotation of Cu-Mo sulfides. Comparative separation parameters between STD (mill
standard), Diesel oil (OD) Esso (25W40 motor lubricant) and Kerosene (K).

Copper Molybdenum
[Oil] Metallurgical True Metallurgical True
Test k, k,
g·t-1 recovery flotation recovery flotation
min-1 in-1
% % % %
STD - 85 63 3.0 73 44 2.2
DO 30 85 64 3.4 73 64 2.3
DO 60 87 64 4.0 76 66 2.2
DO 90 89 68 3.4 78 68 2.3
DO 120 87 66 3.4 75 66 2.6
K 30 85 66 3.4 74 57 2.7
K 60 86 67 4.0 75 51 2.8
K 90 86 68 3.4 75 55 2.9
Esso 25W40 30 87 63 3.6 - - -
Esso 25W40 90 88 63 3.7 - - -

100
Therefore, it is believed that during oil
95 extender, enhanced hydrophobicity and
aggregation of the fines themselves or with
90
coarser particles (carrier) takes place. This
Copper recovery %

85 may explain, the results obtained, higher

recoveries, equal concentrates grades and
80
improved process kinetics. Thus, in this oil
STD
75 extender technique, hydrophobic aggregation
70
Ext-DO 90 g/t would occur after the spreading of the oil at
the collector-coated particles (fines and
65 ultrafines) improving the capture of either the
<5 5-15 15-40 >40
hydrophobic enhanced particles or the
Size fraction, μm
Figure 7: Emulsified Oil (Diesel) Extender Flotation. aggregates (Rubio et al. 2003).
Comparative size-to-size copper recoveries: STD and Moreover, the effect is more effective with
with 90gt-1 Diesel oil. oils having aromatics content, below about 40
% but with naphtenic fractions, and
100 comprising chain lengths of from about 17-
95 about twenty-two carbon atoms. These
90 extender oils had to be highly emulsified and
Molybdenum recovery %

85 are exemplified, in this work by the Diesel Oil

80 and Esso motor oil (Table I). Yet, the effect
75 was not significant with kerosene, light oil
70 without naphtenic groups and low aromatics
65 content. Smitt and Basin (1985), reported
STD Ext-DO 90 g/t
60 similar results for molybdenite and Laskowski
55 and co-workers, for flotation recovery of
50 coarse potash fractions (Laskowski and Dai,
<5 5-15 15-40 >40
1993, Laskowski and Wang, 1997).
Size fraction, μm
Figure 8: Emulsified Oil (Diesel) Extender Flotation.
Comparative size-to-size Molybdenum recoveries: STD 4. CONCLUSIONS
and with 90gt-1 Diesel oil.
Results found in this work showed that
“extender” flotation with emulsified diesel oil
(> 60 gt-1) yielded higher metallurgical

249
efficiencies than the mill standard for copper
and molybdenum sulfides. Concentrate
recoveries increased in about 2-4 %, 3-5 % in
“true” flotation recoveries and between 20-30
% in flotation rate. Size by size, kinetics and
true flotation results proved that metallurgical
gains might be attributed, mainly, to the extra
recovery in the fines (“F”, 37-5 µm) and
ultrafines (“UF”, < 5 µm). These results are
supported by the quality of the laboratory,
especially in the size-by-size tests. Data are
explained in terms of physical aggregation and
hydrophobicity factors that improve the
capture of the smallest particles by bubbles. It
is believed that these results represent real
advances and that this oil based technique will
establish shortly a new basis for the flotation
enhancement of the fine particles.
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