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A Study on Selective Flotation in Low and High Pyritic Copper Sulfide Ores

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A study on selective flotation in low and high

pyritic copper sulphide ores

Ahmad Hassanzadeh & Mohammad Hasanzadeh

To cite this article: Ahmad Hassanzadeh & Mohammad Hasanzadeh (2016) A study on selective
flotation in low and high pyritic copper sulphide ores, Separation Science and Technology, 51:13,
2214-2224, DOI: 10.1080/01496395.2016.1202980

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SEPARATION SCIENCE AND TECHNOLOGY
2016, VOL. 51, NO. 13, 2214–2224
http://dx.doi.org/10.1080/01496395.2016.1202980

A study on selective flotation in low and high pyritic copper sulphide ores
Ahmad Hassanzadeha and Mohammad Hasanzadehb
a
Department of Mineral Processing Engineering, Faculty of Mines, Istanbul Technical University, Istanbul, Turkey; bDrug Applied Research
Center, Tabriz University of Medical Sciences, Tabriz, Iran

ABSTRACT ARTICLE HISTORY

The effect of chemical reagent configurations was investigated on two different copper sulphide ore Received 7 April 2016
types, including high and low pyritic feeds. Three different combinations of collectors as isopropyl-n- Accepted 14 June 2016
ethyl thionocarbamate (C-4132), mixture of mercaptobenzothiazole and butyl sodium dithiphosphate KEYWORDS
(Flomin 7240) and sodium isopropyl xanthate (Z11) were used in flotation experiments. Solely using Chalcopyrite; chemical
C-4132 was selected as the best pattern for both feed types with regard to achieving the highest copper reagent configuration; high
grade and the lowest iron recovery. However, the selectivity index (SI) results showed that the pyritic ore; low pyritic ore;
combination of Z11+F7240 provides the highest selectivity of chalcopyrite against pyrite in either low pyrite
or high pyritic ores.

Introduction flotation process. Ackerman et al. studied the effect of

collectors on copper sulphides and pyrite separation.
Froth flotation is a physicochemical method widely used
They found that N-ethyl-O-isopropyl thionocarbonates
in mineral processing technologies to separate finely
are comparable to those of xanthates.[18] It is also shown
ground valuable minerals from a mixture with gangue
that thinocarbomate and thiourea collectors are more
minerals.[1] In copper sulphide ores, non-valuable iron
selective than xanthates against pyrite and produce better
sulphides (mostly pyrite) are often associated with valu-
separation of chalcopyrite from pyrite in alkaline and
able sulphide minerals (mostly chalcopyrite). These iron
neutral pH conditions.[19,20] Banaei et al. investigated the
sulphide minerals play a significant role on copper flota-
effect of using dithiophophosphate, dithiophosphinates,
tion due to their devastating effect on the quality of
iso-propyl thinocarbomate and xanthates along with their
product and efficiency of process.[2,3] If a mineral surface
combination on increasing the selectivity of chalcopyrite
is covered with hydrophilic species (i.e. iron hydro-
and chalcocite from pyrite.[21] They reported that the high-
xides), a larger amount of collector will be required to
est selectivity in the copper sulphides/pyrite system is
remove the hydrophilic surface species and produce
obtained in the presence of Z200 thinocarbomate mixed
hydrophobic surface on particles. Therefore, in copper
with R407 (a mixture of mercapto benzothiazole (MBT)
flotation process it is essential to take the role of pyrite
and dithiphosphate) and in the presence of isopropyl
into account, not only for being aware of its extremely
xanthate sodium (Z11). Under this condition the copper
detrimental effects on grade and recovery but also parti-
recovery remained almost constant. Recently, Azizi studied
cularly from the environmental point of view, in order to
the order of selectivity performance of collectors (i.e.
reduce SO2 emission through further smelting processes.
sodium isopropyl xanthate, MBT, flomin C4132) and
Recent studies indicate that the selective separation of
their mixtures on the separation of chalcopyrite from pyr-
chalcopyrite from pyrite is very difficult due to the several
ite. It was stated that the order follows the combination of
interactions occurring on the mineral surfaces during the
Z11 and MBTs>flomin C4132>combination of MBTs and
processes of grinding and conditioning.[4,5] Various factors
flomin C4132>combination of Z11, MBTs and flomin
such as the type and quantity of chemical reagents, nature
C4132.[22] Hassanzadeh and Karakas pointed out that the
and structure of minerals, bubble size and its velocity, type
minimum pyrite recovery can be achieved in the presence
of instrumentation and operational variables, surface prop-
of 40 g/t flomin C-4132, 20 g/t methyl isobutyl carbonyl
erty of particles and residence time influence the perfor-
(MIBC), 20 g/t methyl-terminated polypropylene glycol
mance of the flotation process.[6–17] Indeed, the types and
(F742), 200 g/t sodium metabisulphite (SMBS) and at
quantity of the reagents are the most important parts of the

CONTACT Ahmad Hassanzadeh hassanzadeh@itu.edu.tr Department of Mineral Processing Engineering, Faculty of Mines, Istanbul Technical
University, 34469 Istanbul, Turkey.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lsst.
© 2016 Taylor & Francis

a d70 of 70 µm.[23] Vazifeh et al. optimized the dosage and
type of chemical reagents in rougher flotation cells of
Sungun copper mine. The optimum reagent dosages were
found to be 12 g/t Z11, 11 g/t AP407, 3 g/t AF65 and 5 g/t
AF70 to obtain the maximum copper grade (8.17%).[24]
Azizi et al. reported that changing the amount of collector
has intense variation on the kinetics constant of chalcopyr-
ite in the flotation of copper complex ore. The maximum
and minimum flotation rate constants were obtained at
the collector consumption dosages of 30 g/t and 40 g/t,
respectively. In addition, increasing the collector dosage
enhanced ultimate recovery to a certain value and there-
after reduced it .[25] Klimpel showed that when the frother
dosage was held constant while the collector dosage was
increased in the coal flotation process, the flotation rate
increased up to a maximum point and thereafter decreased.
This was reported for several frother types and different
particle size fractions.[26]
Pyrite, FeS2, commonly referred to as fool’s gold, is the
most common sulphide in the Earth’s surface region.
Basically, in the flotation of copper complex ores, a high
pH value is required to separate valuable sulphide minerals
from pyrite or pyrrhotite in the presence of xanthate
collectors.[20] Several works have extensively discussed the
impact of pyrite on copper flotation.[27–30] It has been
reported that, besides its hydrophobic nature in fresh
surfaces, the surface reactions and electrochemical pro-
cesses promote pyrite activation, which are pointed out as
the main reasons for its floatability.[31] Mielczarski et al.
studied the adsorption of xanthate on chalcopyrite.
They stated that the xanthate molecules should be in
contact with a fresh chalcopyrite surface in order to pro-
duce cuprous complex and dixanthogen as a hydrophobic
site.[32] If a mineral surface is covered with hydrophilic
species (i.e. iron hydroxides), a large amount of collector
will be required to remove the hydrophilic surface species
so as to produce a hydrophobic surface on the particles. It
has also been shown that pyrite has a natural floatability,
and that a small percentage can usually be recovered
without a collector.[28,33] Consequently, it can be predicted
that higher rates of its recovery can be achieved through
the use of collectors. Trahar et al. pointed out that the
interactions between sulphide minerals might promote
pyrite floatability. On the other hand, pH values higher
than 11 are essential to extensively depress pyrite in the
presence of xanthate collectors.[34] In the case of coal, over
42 different chemical reagents have been introduced by
many investigators to depress pyrite in the flotation
process, and yet none of them have ever been useful
industrially. This is because, in most cases, the pyrite was
not truly hydrophobic in the first place.[35]
The main purpose of studying the flotation kinetics
is to determine the flotation rate constant and to
SEPARATION SCIENCE AND TECHNOLOGY 2215
analyse the effects of various parameters. Since the
flotation rate constant can be used to simplify and
improve the circuit flow sheets, a number of studies
have been carried out to explain the kinetics of
flotation.[36,37] Ultimate recovery (R∞) and flotation
rate constant (k) are two basic parameters of kinetics
studies. They can be effectively used to evaluate factors
affecting the flotation process. The kinetic rate con-
stant, k, is determined as a function of the dynamical
condition of flotation cells as well as the properties of
minerals. Understanding and interpreting changes in
the values of R∞ and k are very important and can
often be misleading.[38] In practical manner, changing
one condition leads to a change in both R∞ and k
values. This may make it difficult to compare flotation
rate data between tests or to establish a trend for the R∞
and k values under different experimental conditions.
For instance, changing one condition may lead to an
increase in k but a reduction in R∞. However, selectiv-
ity between the valuable and gangue minerals might be
unchanged, increased or decreased depending only on
the combined measure of k and R∞. Therefore in this
study, separation efficiency (S.E.), grade and recovery
as well as selectivity index (SI) are taken into account
for evaluating the S.E. of chalcopyrite from pyrite
within two different ore types.
Despite numerous investigations on porphyry copper
sulphides, there is still lack of knowledge on the selective
flotation of chalcopyrite and pyrite in different ore types.
Generally, grade and recovery are mainly used as
metallurgical criteria to evaluate the performance of
the flotation process. However, other specific indexes
such as S.E. and SI have not been discussed in detail.
The main purpose of this study is to understand the
floatability and separation capability of copper and
iron minerals in two different ores (high and low pyritic
feeds) using several chemical reagent configurations. A
comparison of results has been provided between the
mentioned ore types in terms of obtained copper and
iron grades and recoveries based on three different
metallurgical indexes. In addition, kinetics studies of
chalcopyrite and pyrite minerals have been taken into
account.
Materials and methods
Material, reagents and preparation
In this research, the effect of using different chemical
reagent patterns was studied on two different ore types
(i.e. high pyritic ore type and low pyritic ore type). The
required samples were taken from each ore type
individually. They were chemically analysed and their
2216 A. HASSANZADEH AND M. HASANZADEH

Table 1. Feed analysis of two different ore types.

Component High pyritic ore Low pyritic ore
Cu (%) 0.73 0.94
Fe (%) 6.73 4.55
Mo (%) 0.027 0.026

chemical compositions are presented in Table 1. X-ray

fluorescence (XRF) technique was applied for the ore
characterizations.
Samples were prepared after two stages of laboratory
comminution including crushing and milling. First, the
samples were crushed by a jaw crusher and substantially
homogenized and sealed in special polyethylene bags to
avoid oxidation. Milling was performed on a 1460 g Figure 1. Photomicrograph of a polished section of feed in the
representative sample by a laboratory ball mill (the stan- high pyritic ore type.
dard bond ball mill). Lime (CaO) was applied as a pH
regulator in the flotation experiments. Different combi-
nations of isopropyl-n-ethyl thionocarbamate 95%
((CH3)2CHOCSNHC2H5, abbreviated C-4132), mixture
of mercaptobenzothiazole (MBT) and dithiphosphate
(MBT/DTP, so-called F7240) and sodium isopropyl
xanthate 90% (C4H7NaOS2, abbreviated Z11) were
used as collectors, which were supplied by Cytec chemi-
cals. Polypropylene glycol (H[OCH(CH3)CH2]nOH,
abbreviated as F742) and pine oil (PO) were used as
frothers with the same dosages in the flotation examina-
tions, which were also provided by Cytec chemicals.

Figure 2. Photomicrograph of a polished section of feed in the

Mineralogical analysis low pyritic ore type.

Polished sections of the selected samples were prepared

by mixing 1 g of the sample with 10 g of the moulding
powder. The blended mixture was then pressed and har-
dened in the sample maker equipment under the pressure
of 4200 Pa and temperature of 140ºC for 20 min. Leica
(DM-LP) microscope was used for the determination of
liberation degree. In this study, samples were taken from a
porphyry copper sulphide ore. Chalcopyrite was identi-
fied as the main copper mineral, whereas pyrite and
silicate minerals were recognized as the main problematic
sulphide and non-sulphide gangue minerals, respectively.
Figure 1 presents the mineralogical micrograph of the
sample in the high pyritic feed. It can be observed that
the pyrite is the most predominant mineral among others
due to the natural characteristic of the feed.
Quantitative X-ray diffraction technique (SQ-XRD)
was applied to determine the proportion of each
mineral in the ore. According to the results it can be
observed that the main precious copper mineral is
chalcopyrite while the non-valuable sulphide mineral
is pyrite (Table 2).
Figure 2 displays the mineralogical status of the
studied ore in the case of low pyritic feed. As seen,
the frequency of the pyrite and chalcopyrite minerals in
this ore type is quite different from that in Fig. 1 (i.e.
high pyritic feed). In addition, chalcopyrite has the
highest proportion between the disseminated minerals
in the low pyritic feed. However it is obviously shown
that the distribution of pyrite mineral in this ore type is
significantly lower than that in the high pyritic ore.
Flotation experiments
Batch flotation experiments were carried out using a
Denver flotation machine (D12) with the impeller

Table 2. Mineralogical composition of the feed using SQ-XRD analysis method.

Mineral Covellite (CuS) Chaclopyrite (CuFeS2) Pyrite (FeS2) Goethite (FeOOH) Hematite (Fe2O3) Non-sulphide gangue minerals
Percent (%) 2 54 7 3 3 30

Figure 3. Schematic process of conducting flotation experiments.
speed of 1400 rpm in a 4.3 L flotation cell. The pulp
density was adjusted to 28% solids at the beginning of
each test. To adjust the slurry pH at 11.8, CaO was
added to the cell. Then collector(s) and frothers were
added with corresponding conditioning times of 1 and
2 min, respectively. Thereafter, air was opened and
flowed inside the cell and the collection of the froth
was started (Fig. 3). In the flotation kinetics tests, the
concentrate froth samples were collected at the intervals
of 1, 2, 3, 5, 8, 12 and 16 min. The flotation froth was
scraped every 10 s. Eventually, the concentrate and
tailing samples were filtered, dried and assayed.
Three different chemical configurations were used
associated with the flotation experiments. In this regard,
reagent type and dosages are shown in Table 3. It has to
be noted that in all three chemical patterns, collector and
frother dosages were kept constant as 40 g/t and 30 g/t,
respectively. However, only their combinations and con-
figurations were changed. Azizi studied the role of col-
lector dosage on cumulated recovery versus time curves
of copper and iron. He found out that using 40 g/t
collector dosage for the copper flotation presents better
overall flotation performance.[22] In addition, with
regard to the constant type and dosage of the frothers,
the differences between chemical patterns only refer to
the various combinations of consumed collectors.
Therefore the diversity in copper and iron flotation
characteristics using the different chemical configura-
tions can be merely attributed to the variation of
collector type and dosage.
Evaluation of the flotation process
Three different indexes (i.e. grade and recovery, S.E.
and SI) were used to evaluate the obtained results of the
flotation experiments.
Table 3. Applied different chemical reagent configurations to
the flotation experiments including chemical reagent types and
dosages.
C-4132 Z11 F-7240 F-742 PO
Configuration (g/t) (g/t) (g/t) (g/t) (g/t)
I 0 15 25 15 15
II 40 0 0 15 15
III 15 10 15 15 15
SEPARATION SCIENCE AND TECHNOLOGY 2217
In order to evaluate the performance of flotation
experiments and to study the influence of reagents,
recovery of copper and iron was calculated using the
mass balance method described by Wills according to
the following formula[1]:
Cc
R¼  100 (1)
ðC þ TÞ  f
where R is recovery, C is dry weight of concentrate,
c is % grade of concentrate, T is dry weight of
tailing and f is feed grade.
However, there is a problem in quantitatively asses-
sing the technical performance of a floatation process
whenever the results of two similar test runs are com-
pared. If both the grade and recovery are greater for
one case than the other, then the choice of process is
simple, but if the results of one test show a higher grade
but a lower recovery than the other, then the choice is
no longer obvious. There have been many attempts to
combine recovery and grade into a single index defin-
ing the metallurgical efficiency of the separation. These
have been reviewed by Schulz, who proposed the S.E.
index as follows:
S:E: ¼ Rm  Rg (2)
where Rm is the recovery of the valuable mineral and Rg
is the recovery of the gangue into the concentrate.
Assuming c, f and t are % grade of concentrate, feed
and tailing, respectively, C is the fraction of the total
feed weight that reports to the concentrate and m is
the percentage metal content of the valuable mineral;
therefore S.E. can be defined as follows:
Cc 100Cðm  cÞ
S:E: ¼ Rm  Rg ¼ 100 ½ 
f ðm  f Þ
100Cmðc  f Þ
¼ (3)
f ðm  f Þ
SI is another criterion to evaluate the flotation
experiments. Xu suggested a modified rate constant
KM, which is a combination of infinitive recovery
(R∞) and flotation kinetic rate (k), which is given by
the following equation[39]:
KM ¼ R 1  k (4)
2218 A. HASSANZADEH AND M. HASANZADEH
The modified rate constant KM is the rate of the
reaction at time t = 0.
According to Xu,[39] the modified rate constants
were used to define a new quantity, SI, or the relative
rate constant of one mineral (M1) over the other
mineral (M2). It is the ratio of the modified rate con-
stant of mineral M1 to the modified rate constant of
mineral M2. Consequently, SI is introduced by Eq. (9).
KM 1
SIðM1 =M2 Þ ¼
KM 2
In fact, SI is the quantification of the selectivity of a
collector for a particular mineral over the other under a
given set of process variables. Factors having a positive
effect on SI have to be identified to maximize the
separation between two minerals.
In this study, SI between Cu and Fe was calculated as
follows:
KMCu
SIðCu=FeÞ ¼
KMFe
where KMCu and KMFe are the modified rate constants
of copper and iron, respectively.
Result and discussion
Grade and recovery of chalcopyrite and pyrite
Figure 4 shows the effect of using three different che-
mical reagent patterns on copper and iron grades in
both high and low pyritic ore types. It can be seen that
the obtained iron grades from both feed types are
roughly the same in terms of employing configurations
I and III. In other words, despite the ore type being
high pyritic feed, configurations I and III have the same
iron grade because of the low pyritic feed . Therefore, if
the ore type turns out from the low pyritic feed to the
high pyritic one, iron grade in concentration will be
constant with the use of collector(s) irrespective of
40
30
Iron Grade (%)
20
10
0 0
0 1
Configuration
Figure 4. The variation of copper and iron grades as a function of chemical reagent configurations in the flotation of both low and
high pyritic ore types.
whether Z11 or a combination of Z11+F7240+C4132
is used. In addition, it can be stated that using different
chemical configurations has relatively no significant
effect on iron grade in the high pyritic feed. However,
configuration II profoundly diminishes the iron grade
in the low pyritic feed.
Evidently it is seen that the resultant copper grade of
the low pyritic feed using each configuration is greater
than that in the high pyritic feed. Moreover, the second
(5) pattern shows the capability of achieving the maximum
copper grade for both feed types. It denotes that using
the collector flomin-C4132 has a notable effect on the
copper grade either in low or high pyritic ore types.
Also, it has no meaningful influence on the iron grade
of the high pyritic feed while it dramatically declines
the iron grade of the low pyritic feed. This might be
relevant to the difference in the liberation degree of the
minerals in the ore types and/or the undesirable effect
of increasing pyrite content within the high pyritic feed.
(6) Because the main copper mineral in the studied ore
types is chalcopyrite, copper floatability can be directly
referred to the chalcopyrite . It is also concluded that
the chalcopyrite from massive and finely disseminated
sulphide ores has different flotation properties. The
floatability of chalcopyrite is highly dependent on the
presence of oxygen in the pulp (i.e. aeration), pH of the
pulp and the type of collector. Therefore, it is reported
that chalcopyrite floats much better with dithiopho-
sphate and thionocarbamate collectors in comparison
with using xanthate.[40,41]
Figure 5 illustrates the effect of using three different
chemical reagent configurations on copper and iron
recoveries in both low and high pyritic ore types. It can
be obviously observed that utilizing different collector
combinations as Z11+F7240 (configuration I), C4132
(configuration II) and C4132+F7240+Z11 (configura-
tion III) displays various consequences on the iron
recovery. In fact, configuration II gives the lowest iron
recovery for both ore types, which is quite desirable for
40
Low pyritic feed Low pyritic feed
High pyritic feed High pyritic feed
30
Copper Grade (%)
20
10
2 3 4 0 1 2 3 4
Configuration
 SEPARATION SCIENCE AND TECHNOLOGY 2219

100 100

80 80

Copper Recovery (%)

Iron Recovery (%)
60 60

40 40

20 20
Low pyritic feed Low pyritic feed
High pyritic feed High pyritic feed
0 0
0 1 2 3 4 0 1 2 3 4

Configuration Configuration

Figure 5. Effect of using three different chemical reagent patterns on copper and iron recoveries in the low and high pyritic feeds.

chalcopyrite flotation. In spite of that, C4132 (i.e. con- galvanic interactions occurring between pyrite and chal-
figuration II) does not have any significant effect on iron copyrite surfaces during grinding and conditioning,
grade in the case of high pyritic feed, while it decreases prior to the flotation, lead to chalcopyrite oxidation
the iron recovery dramatically. Another fact is that since and copper activation of the former. This also results in
the obtained iron grade and recovery results using con- the formation of hydrophilic surface coatings of iron
figurations I and III are relatively close for both ore hydroxide species that inhibit chalcopyrite flotation.
types, using the combination of collectors F7240+Z11 Copper activation of pyrite increases collector adsorp-
and C4132+F7240+Z11 presents in some manner a tion onto the pyrite surface, promoting its flotation,
similar influence on copper recoveries. which subsequently reduces the overall chalcopyrite
With regard to changing the ore type from low pyritic recovery and grade.[42,43]
to high pyritic, using each configuration individually According to the results obtained from the overall
denotes no significant effectiveness on copper recovery. flotation experiments, which are shown in Figures 4
Furthermore, according to the observed results, it can be and 5, it can be concluded that configurations I and III
stated that irrespective of whether high or low pyritic (i.e. Z11+F7240 and C4132+F7240+Z11, respectively)
feeds are used, roughly the same iron recovery can be imply relatively similar effect on copper and iron float-
recognized by the use of different collector combina- ability characteristics (grade and recovery). Therefore,
tions. However the outcomes for the copper grade and one of them is chosen in order to simplify the kinetics
recovery using the low pyritic feed are always higher studies for both ore types. Finally, configurations I and II
than those in the high pyritic one, which has been were selected for further detailed investigation in terms
obviously expected. Banaei et al. showed that in the of SI and S.E.
presence of Z11, copper recovery remains almost
constant.[21] It is in good agreement with the obtained
Flotation kinetics parameters and SI
results of copper recovery in our investigation. They also
found that increasing the concentration of Z200 had not Figure 6 displays the kinetics behaviour of copper and
changed the copper recovery significantly; however, iron iron as a response of chemical configuration patterns in
recovery was decreased. In addition, it is shown that the high pyritic ore type. Among all the proposed

100 100
Configuration I
Configuration II
80 80 Classic Model-Config.I
Classic Model-Config.II
Copper Recovery (%)

Iron Recovery (%)

60 60

40 40

20 Configuration I 20
Configuration II
Classic Model-Config.I
Classic Model_Config.II
0 0
0 2 4 6 8 10 12 14 16 18 0 2 4 6 8 10 12 14 16 18
Time (min) Time (min)

Figure 6. Flotation kinetics of chalcopyrite and pyrite in high pyritic ore type with regard to using two different chemical
configurations.
2220 A. HASSANZADEH AND M. HASANZADEH

flotation models, the classical first-order flotation
model is the most widely used.[44] The model agrees
very well with the experimental data of copper and iron
recoveries. In addition, it is usually selected for the
estimation of kinetics rates (k) and ultimate recoveries
(R∞). Therefore, in this case the order of flotation
reaction (n) is assumed equal to one, which is shown
as Eq. (7).
R ¼ R1 ð1  expðktÞÞ
where R is the cumulative recovery after time t (min),
k is the first-order rate constant (1/time) and t is the
cumulative flotation time.
Copper-pyrite separation usually occurs at the
rougher flotation stage via enhancing the pulp pH to
greater than 9, which is performed in the conducted
flotation tests. Therefore, pyrite tends to be strongly
depressed due to the hydrophilic surface produced by
the presence of hydroxyl ions in the pulp.[45,46]
Consequently, it can be observed in Fig. 6 that the iron
recovery values versus time are considerably lower than
the copper recovery values versus the corresponding
time values.
According to the cumulative copper recoveries as a
function of time along with the mentioned detailed
results in Table 3, it can be stated that using configura-
tion I supplies both higher kinetics rate and more
infinitive recovery compared to configuration II. It
means despite flomin-C4132 providing higher copper
grade and lower pyrite recovery (Figs. 4 and 5), the
estimated kinetics rate and infinitive recovery of copper
using the combined collectors of Z11+F7240 are greater
than flomin-C4132. In addition, it is seen that even
though a higher pH value (i.e. pH>11) was used in
the flotation experiments to separate valuable copper
sulphide minerals from pyrite, still pyrite particles
floated. One of the important effective factors of this
phenomenon is the positive effect of xanthate concen-
tration on pyrite flotation.[47] Besides the natural
hydrophobicity of pyrite in fresh surfaces, the surface
reactions and electrochemical processes promote pyrite
activation, which is pointed out as the main reason for
its floatability.[31] It is also proved that both activated
and bare pyrite surfaces interact with thiol collector
molecules such as xanthates and increase the floatabil-
ity of pyrite.[48]
Figure 7 shows the kinetics flotation results of copper
and iron in the low pyritic ore type using two different
(7) collector combinations (i.e. configuration I (Z11+F7240)
and configuration II (flomin-C4132)). High kinetic rates
of copper in both configurations in the low pyritic ore
type compared to their corresponding values in the high
pyritic feed are quite evident. As seen from Fig. 7 and
Table 3, copper kinetic rates in configurations I and II
are 0.82 and 0.52 1/min, respectively, whereas the related
values in the high pyritic feed are 0.44 and 0.3 1/min,
respectively.
Table 4 represents the kinetic rates and infinitive recov-
eries of copper and iron from the kinetic flotation tests in
both high and low pyritic feeds. To estimate the kinetic
parameters, a first-order flotation model was utilized. It is
seen that the kinetic rates of copper and iron in the low
pyritic feed are higher than those in the high pyritic one. In
addition, the obtained ultimate copper recovery of the low
pyritic feed is greater than that in the high pyritic feed while
infinitive recovery of iron in the low pyritic ore type is
lower than that in the high pyritic one.
It can be also seen that configuration I provides a
stronger copper kinetics rate compared to configuration
II. However, it is not correct for the case of iron. In fact, in
Table 4. Resultant flotation kinetics parameters for both ore
types using the first-order flotation kinetics model.
High pyritic ore type Low pyritic ore type
Cu Fe Cu Fe
k R∞ k R∞ k R∞ k R∞
Configuration I 0.44 80.43 0.12 62.06 0.82 88.82 0.15 52.87
Configuration II 0.30 78.54 0.09 28.45 0.52 88.42 0.40 22.35

100 100
Configuration I
Configuration II
Classic Model-Config.I
80 80 Classic Model-Config.II
Copper Recovery (%)

Iron Recovery (%)

60 60

40 40

Configuration I
20 Configuration II 20
Classic Model-Config.I
Classic Model-Config.II
0 0
0 2 4 6 8 10 12 14 16 18 0 2 4 6 8 10 12 14 16 18
Time (min) Time (min)

Figure 7. Experimental results of flotation kinetics of copper and iron in the low pyritic ore type versus two different chemical
reagent configurations.
 SEPARATION SCIENCE AND TECHNOLOGY 2221

the high pyritic feed when the combination of Z11+F7240 of selectivity of chalcopyrite from pyrite using chemical
is used, the iron kinetic rate is slightly higher than configuration I in the low pyritic feed is around a couple
using only flomin-C4132. However, in the case of the of times more than that in the high pyritic ore type. In the
low pyritic ore type using configuration II provides same condition, using configuration II provides nine
much a greater kinetics rate for iron in comparison with times higher selectivity for chalcopyrite flotation. Within
that in configuration I. Furthermore, configuration I each individual ore type, SI of configuration I is more
supplies higher copper and iron infinitive recoveries than that using configuration II. In other words, although
than configuration II in either low or high pyritic feeds. it is proved that thionocarbonates (e.g. flomin C-4132) are
Agar flotation kinetics model was selected to esti- comparable to xanthates (e.g. Z11), in this case study the
mate the kinetic parameters for SI. Agar considered two combination of Z11+F7240 gives more SI compared to
phenomena, which are opposite in their action in using merely flomin C-4132. In a very similar study,
affecting the flotation kinetics. Some solids in the slurry Azizi recently pointed out that SIs for flotation of copper-
are naturally hydrophobic and will have air bubbles sulphide ore are in the order of Z11+MBT>C4132>MBT+
attached to them during the conditioning period. C4132>Z11+MBT>C4132.[22] It can be observed that
Hence, their flotation starts even before starting the there is a good agreement between our achievements
air flow.[49] On the other hand, when air flow is started, and the reported results of the investigation.
several seconds elapse before a full depth of loaded
froth is present in the flotation cell. The first phenom-
S.E. index
enon gives a negative time correction while the second
amounts to a positive time correction. Hence, Agar Figure 8 shows the S.E. results regarding the flotation
introduced a time correction factor, b, in the equation kinetic experiments of copper and iron in the high
related to the first-order flotation kinetics (Eq. 7).[50] pyritic ore type using two different collector combina-
The time correction factor is added because of the tions. As seen, configuration I implies using 15 g/t Z11
difficulty in physically assigning time zero. The mod- and 25 g/t F7240 while configuration II represents
ified rate equation is using only 40 g/t flomin C-4132. Frother type and its
dosages were exactly the same in both the chemical
R ¼ R1 ð1  expðkðt þ bÞÞÞ (8) reagent patterns as 15 g/t PO and 15 g/t F742.
Therefore different results in the S.E. values can be
As shown in Table 5, kinetic parameters are calculated
attributed to the combination of the consumed collec-
based on the Agar flotation kinetics model for both cop-
tors. It can be seen that the S.E. values for copper are
per and iron in either low or high pyritic feeds. According
always higher than those for iron. One possible reason
to Natarajan and Nirdosh, SI is the quantification of the
is attributed to the kinetics rate differences between
selectivity of a collector for a particular mineral over the
copper and iron as well as their surface characteristics
others under the given set of process variables.[51] The
in the adsorption of reagents for covering hydrophobic
obtained results of SI show that the separation feasibility
layer on their surfaces. According to Fig. 8, the S.E.
of copper from pyrite in the low pyritic ore is greater than
values of copper and iron increase very quickly in
that in the high pyritic one. It implies that the probability
initial time intervals, whereas with passing the flotation
time, it remains constant for iron and decreases slightly
Table 5. Predicted selectivity index values and estimated for copper. It is evident that the resultant S.E. values
kinetic properties of both ore types using the Agar model. between copper and iron reveal a greater difference for
Configuration I Configuration II configuration II (Fig. 8b) compared to the results of
High pyritic ore Cu R∞ 80.90 Cu R∞ 80.57
k 0.41 k 0.25 configuration I (Fig. 8a). In other words, using Flomin
b 0.10 b 0.31 C-4132 supplies better separation feasibility between
Fe R∞ 62.66 Fe R∞ 31.01
k 0.12 k 0.08 copper and iron minerals within the ore compared to
b 0.00 b 0.29 applying the combination of Z11 and F7240. In addi-
kMcu 33.29 kMcu 20.39
kMFe 7.301 kMFe 2.43 tion, according to Figs. 8a and 8b, it can be concluded
SI 4.56 SI 0.66 that the main separation between chalcopyrite and pyr-
Low pyritic ore Cu R∞ 88.86 Cu R∞ 88.46
k 0.81 k 0.51 ite occurs in the first 2 min of the flotation kinetic test
b 0.01 b 0.01 and subsequently it keeps constant.
Fe R∞ 59.44 Fe R∞ 25.15
k 0.12 k 0.30 Figure 9 illustrates the S.E. values of copper and iron in
b 0.01 b 0.01 the low pyritic feed as a function of two mentioned differ-
kMcu 72.33 kMcu 45.51
kMFe 7.31 kMFe 7.59 ent collector combination patterns (i.e. configurations I
SI 9.89 SI 5.99 and II). As seen in Fig. 9a, the maximum achievable S.E.
2222 A. HASSANZADEH AND M. HASANZADEH

100 100

80 80

60 60

S.E. (%)

S.E. (%)
40 40

20 20
Cu Cu
A Fe B Fe
0 0
0 2 4 6 8 10 12 14 16 18 0 2 4 6 8 10 12 14 16 18
Time (min) Time (min)

Figure 8. Separation efficiency (S.E.) of copper and iron in high pyritic ore type versus two different chemical reagent patterns: A)
configuration I and B) configuration II.

100 100

80 80

60 60
S.E. (%)

S.E. (%)
40 40

20 20
Cu Cu
A Fe B Fe
0 0
0 2 4 6 8 10 12 14 16 18 0 2 4 6 8 10 12 14 16 18
Time (min) Time (min)

Figure 9. Separation efficiency (S.E.) of copper and iron in the low pyritic ore type versus two different chemical reagent patterns: A)
configuration I and B) configuration II.

of iron is 42% using configuration I, while it can reach 20% Conclusions

by means of configuration II. Indeed, using flomin C-4132
In this study three different indexes were utilized to
rather than a combination of Z11+flomin C-4132 implies a
evaluate the selectivity of copper-pyrite flotation in low
better yield in the low pyritic feed. S.E. values of copper
and high pyritic copper sulphide ores. Grade and
promptly decrease using the combination of Z11+F7240.
recovery, S.E. and SI were taken as the metallurgical
However it shows a constant trend as a function of time for
criteria for assessment of the flotation batch results.
configuration II. Reducing copper recovery can be attrib-
Flotation experiments along with kinetics studies were
uted to the formation of stable hydrophilic metal oxide/
used with different chemical reagent configurations in
hydroxides coatings on the chalcopyrite surface, thereby
order to observe the effect of each reagent pattern on
minimizing or preventing the adsorption of collector onto
chalcopyrite and pyrite floatabilities. In each chemical
the chalcopyrite surface. Such surface oxide/hydroxide spe-
regime standard values of 40 g/t collector(s) and 30 g/t
cies decrease the chalcopyrite hydrophobicity and collector
frothers were used regarding configuration I (15 g/t
adsorption, thereby impacting the flotation response of the
Z11, 25 g/t F7240, 15 g/t F742 and 15 g/t PO), config-
mineral. Koleini et al. studied the effect of applying differ-
uration II (40 g/t C-4132, 15 g/t F742 and 15 g/t PO)
ent depressant systems (i.e. sodium cyanide-zinc sulphate
and configuration III (15 g/t C-4132, 10 g/t Z11, 15 g/t
and dextrin-zinc sulphate) on chalcopyrite-pyrite separa-
F7240, 15 g/t F742 and 15 g/t PO). With regard to the
tion by the flotation process in Taknar deposit (Cu-Az-Au-
obtained S.E. values and grade and recovery results, it
Ag-Pb). They found that sodium cyanide is a suitable
was found that configuration II provides the best selec-
depressant for the pyrite in the first stage of flotation.
tivity for both high and low pyritic ore types. The SI
However, compared to dextrin, the chalcopyrite recovery
values showed that the first configuration is the best
reduced around 2% using sodium cyanide. Mixed collector
one. Furthermore, the obtained results of the SIs
system as Aero238+SIPX and TC1000+SIPX denoted a
denoted that the selective feasibility for chalcopyrite
comparable performance for selectivity of chalcopyrite
flotation in the low pyritic ore type is higher than that
against pyrite.
in the high pyritic ore.

Using C-4132 was very effective for obtaining the
maximum copper grade in both high and low pyritic
feeds. Nevertheless, it showed no significant effect on
copper recovery. Moreover, it reduced the iron grade
of the low pyritic ore while it did not have any influence
on that in the high pyritic feed. Besides that, it dramati-
cally decreased the iron recovery for both ore types. It
was found that the given configurations I and III provided
relatively similar effects on iron grade and recovery
in both high and low pyritic ores. However their influ-
ences on copper grade and recovery were significantly
different. In other words, using either of the combined
collectors 15 g/t Z11+25 g/t F7240 or 5 g/t C4132+15 g/t
F7240+10 g/t Z11 with the same frother types and dosages
(i.e. 15 g/t PO and 15 g/t F742) had no considerable effect
on iron grade and recovery. It was also concluded that for
the evaluation of selective separation of copper-pyrite
ores, attending to the grade-recovery or S.E. results is
not sufficient and the estimated SI values should be highly
taken into consideration.
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