Minerals Engineering xxx (2012) xxx–xxx

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Minerals Engineering
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A novel approach for preferential flotation recovery of molybdenite from a porphyry

copper–molybdenum ore
Liu Guang-yi a,b,⇑, Lu Yi-ping c, Zhong Hong a,b,⇑, Cao Zhan-fang a, Xu Zheng-he d
a
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China
b
Key Laboratory of Resources Chemistry of Nonferrous Metals, Central South University, Ministry of Education, Changsha 410083, China
c
School of Resources Processing and Bioengineering, Central South University, Changsha 410083, China
d
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Canada T6G 2V4

a r t i c l e i n f o a b s t r a c t

Article history: In this paper, three flotation approaches, bulk flotation followed by separation, selective Cu flotation fol-
Available online xxxx lowed by bulk flotation and then separation, and preferential Mo flotation followed by Cu flotation, were
investigated to concentrate molybdenite from Dexing (Jiangxi Province, China) porphyry Cu–Mo ores. The
Keywords: bench-scale flotation results demonstrated that compared to other two flotation approaches, the prefer-
Sulfide ores ential Mo flotation approach using a new non-thiol collector obtained a high recovery of molybdenite in a
Froth flotation molybdenum circuit, while the tailing of molybdenum circuit was treated by a copper flotation circuit to
Non-ferrous metallic ores
obtain a high recovery of other co-present metal values. The industrial flotation tests indicated that com-
Flotation collectors
pared to the bulk flotation approach, the preferential Mo flotation approach achieved an excellent cleaner
concentrate containing 0.655% Mo with 88.49% Mo recovery, and increased Mo recovery and grade over
34.0% and 0.4% in the molybdenum circuit, respectively. For being uncontaminated with thiol collectors,
this cleaner concentrate was readily treated to perform the Mo/Cu flotation separation which returned a
superior Mo concentrate containing 48.83% Mo with 90.60% Mo operation recovery as well as saved about
1/2 Na2S consumption.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction unchanged or improved only marginally. Bulatovic et al. (1998) re-

Approximately 50% of the world’s molybdenum production
comes from Cu–Mo ore as a by-product (Bulatovic, 2007). The flo-
tation recovery of molybdenite from porphyry Cu–Mo ore is con-
sistently lower than that of the copper sulfides (Bulatovic et al.,
1998; Bulatovic, 2007; Triffett et al., 2008). In 2004, the price of
molybdenum increased near 10-fold resulting in a renewed
emphasis on production of this metal, including efforts to optimize
its flotation recovery (Triffett et al., 2008).
Shirley and Sutulov (1985) and Hernlund (1961) summarized
some of the factors that might affect the floatability of molybde-
num from porphyry copper ores at industrial scale; these are: (1)
mineralogy of ore deposits, (2) slime coatings, (3) optimizing cop-
per metallurgy at the expense of molybdenum, (4) grinding and
liberation, and (5) flotation reagents. Ametov et al. (2008) found
the decrease in the flotation feed density considerably improved
recovery of molybdenite, while copper recovery either remained
⇑ Corresponding authors. Address: College of Chemistry and Chemical Engineer-
ing, Central South University, Changsha 410083, China. Tel.: +86 731 88830654;
fax: +86 731 88879616.
E-mail addresses: guangyiliu@csu.edu.cn (G.-yi. Liu), zhongh@csu.edu.cn
(H. Zhong).
vealed clay minerals had significant influence on the flotation
recovery of copper and molybdenum from many Chilean porphyry
copper ores. Based on size recovery data, quantitative mineralogy
and surface analysis in the Copperton bulk flotation circuit, Triffett
et al. (2008) proposed several operational changes to enhance the
molybdenum recovery which included the separate treatment of
an ore type containing problematic silicate minerals and the opti-
mization of the frother to collector ratio to ensure adequate froth
stability. Chander and Fuerstenau (1972) found the molybdenite
floatability was strongly affected by surface oxidation, and calcium
ions exhibited a strong affinity to adsorb onto molybdenite surface
and were able to reverse its zeta potential. Raghavan and Hsu
(1984) considered heterocoagulation of molybdenite and quartz
particles was inevitable in solutions containing large amounts of
lime, which impaired the floatability of molybdenite. They also
found coarse molybdenite particles (120  200 mesh) float extre-
mely rapidly and completely without being influenced by hetero-
coagulation, but the flotation of fine molybdenite particles
(minus 200 mesh) was sensitive to particle size and heterocoagula-
tion, and overgrinding of molybdenite created very rough surfaces
to reduce its floatability.
Smit and Bhasin (1985) discovered that a two-component blend
of a higher molecular-weight petroleum hydrocarbon and a lower

0892-6875/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2012.02.008

Please cite this article in press as: Liu, G.-y., et al. A novel approach for preferential flotation recovery of molybdenite from a porphyry copper–molybde-
num ore. Miner. Eng. (2012), doi:10.1016/j.mineng.2012.02.008
2 G.-y. Liu et al. / Minerals Engineering xxx (2012) xxx–xxx
molecular-weight diluent oil could be a better molybdenite collec-
tor than a single component of higher molecular-weight oil. Fur-
thermore, the flotation oils blended from naphthenic base stock
gave superior flotation results whereas those blended from aro-
matic stock resulted in inferior molybdenite flotation. Bulatovic
(2007) summarized the low-viscosity oils gave lower recoveries
than the high viscosity oils but at a somewhat higher concentrate
grade, aromatic alcohols (i.e. pine oil) and alkoxy paraffin gave bet-
ter MoS2 recovery than straight alcohol (MIBC) or glycol, and the
use of emulsifier improved molybdenum recovery significantly.
Hansen and Klimpel (1988) designed mixed C4–C7 alcohols plus
hydrocarbon oil for copper–molybdenum sulfide flotation. Frothers
consisting of propylene oxide and aliphatic alcohols were effective
in recovering very coarse mineral particles, and branched alcohols
with propylene oxides could improve selectivity over fine particles
(Klimpel, 1988; Xia and Peng, 2007).
There are several flow sheets (listed in Fig. 1a and b) used in the
flotation recovery of copper and molybdenum from their porphyry
sulfide ores. Fig. 1a is a typical flow sheet that consists of two
stages (Raghavan and Hsu, 1984; Bulatovic, 2007; Liu et al.,
2011). The first stage, commonly known as the copper circuit, pro-
duces a bulk copper sulfide–molybdenum sulfide concentrate. The
second stage subjects the bulk copper–molybdenum sulfide con-
centrate to a selective flotation technique to separate molybdenite
from copper sulfide. In the copper circuit, typically 1–4 kg/ton of
lime is added to maintain an alkaline pH for the depression of pyr-
ite. The calcium species releases into the solution from the lime
could impair the floatability of molybdenite through adsorption
(Chander and Fuerstenau, 1972; Raghavan and Hsu, 1984; Liu
et al., 2011). Compared to sodium butyl xanthate, a selective
collector N-propyl-N-ethoxycarbonyl thiourea (PECTU) decreased
2/3 lime consumption in the flotation separation of Cu/Fe sulfide
minerals in Dexing copper mine, and increased the Mo grade and
recovery in the copper cleaner concentrate (Liu et al., 2011).
Fig. 1b is another flow sheet introduced by Malhotra et al.
(1986) to obtain a relatively high recovery of molybdenite. The
character of this flotation process is that it includes a rougher flo-
tation step in which no collector (only frothers) is used. It can ob-
tain a relatively high recovery of molybdenite in a rougher
concentrate uncontaminated with collectors, which rougher con-
centrate can be cleaned to yield a high-grade product while the
rougher tailing can be treated by flotation to obtain high overall
recovery of molybdenite along with a high recovery of other co-
present metal values. Fig. 1b has also been adopted by Dexing cop-
per mine. While in the rougher flotation step, a selective collector
thionocarbamate is used for preconcentration of copper and
molybdenum from porphyry copper ores, which can reduce the
influence of lime on the floatability of molybdenite and obtain rel-
atively high overall recovery of molybdenite. However, it needs
recovery molybdenite from the copper circuit (see Fig. 1b), and
the floatability of molybdenite has to be impaired by the lime used
in the flotation separation of Cu/Fe sulfide minerals.
In the present study, a novel flow sheet and high effective col-
lectors for molybdenite flotation will be investigated to improve
molybdenite recovery from Dexing (Jiangxi Province, China) por-
phyry Cu–Mo ores. The designed flow sheet includes a molybde-
num circuit and a copper circuit. In the molybdenum circuit, a
non-thiol collector and a Mo/Cu preliminary separation operation
is used to obtain a high recovery of molybdenite in a cleaner con-
centrate uncontaminated with thiol collectors, which cleaner con-
centrate can easily be cleaned to yield a high Mo recovery product
with a low consumption of Na2S during Mo/Cu flotation separation.
Then the rougher tailing of the molybdenum circuit will be treated
by the copper circuit to obtain a high recovery of copper along with
a high recovery of other co-present metal values. Through this flo-
tation process, the influence of lime on molybdenite floatability is
Please cite this article in press as: Liu, G.-y., et al. A novel approach for preferential flotation recovery of molybdenite from a porphyry copper–molybde-
num ore. Miner. Eng. (2012), doi:10.1016/j.mineng.2012.02.008
remarkably impaired and the high recovery of molybdenite will be
obtained.
2. Experimental methods
2.1. Material and reagent
2.1.1. Process mineralogy
The test material are porphyry copper ores from the Dexing
copper mine of Jiangxi Province in China, and the copper bearing
minerals are chalcopyrite, chalcocite, digenite, covellite, tetrahe-
drite, tennantite, bornite, as well as some oxide copper minerals
such as malachite and cuprite. The main iron bearing minerals
are pyrite and marcasite. The molybdenum form is molybdenite
and the gold forms are native gold and electrum. The significant
amounts of non-sulfide gangue minerals are quartz, sericite, chlo-
rite, illite, carbonates and biotite.
Based on electron probe and chemical analysis, molybdenite in
Dexing copper mine contains 60.0% Mo, 39.8% S, and other trace ele-
ments such as Re, Se and Ag. In rocks, molybdenite commonly inter-
grows with quartz, carbonates, anhydrite, pyrite, chalcopyrite, etc.
Molybdenite exists two modes of occurrence in Dexing porphyry
copper ore. One is an automorphic–hypautomorphic and dissemi-
nated flake aggregation, which flake diameters are typically in the
range of 0.05–0.1 mm, sometimes over 1 mm. The other is a mixed
polymorph of hexagonal and trigonal molybdenite, which has weak
floatability and is difficult to recovery by flotation approach.
In rocks, molybdenite commonly disseminates in the gangue
non-sulfide minerals. The primary grind employed is to liberate
molybdenite from these non-sulfide minerals. When a grind of
about 65% minus 76 lm is used, the liberation of molybdenite is
only about 50% to the whole minerals, but about 70–90% to the
non-sulfide minerals. When a regrind of about 95% minus 76 lm
(near 68% minus 38 lm) is used, the liberation of molybdenite is
over 93%.
2.1.2. Ore samples
Two kinds of ore samples were used in the bench-scale flotation
test. One was called as normal ore with 4.12% CuO, and the other
was called as high-oxided ore with 13.26% CuO. These ore samples
were taken from different deposits of Dexing Copper Mine, and
their head assay was presented in Table 1.
2.1.3. Reagents
The reagents used in the bench-scale flotation tests and their
product names were listed in Table 2, and the reagents were used
as received.
2.2. Flotation tests
2.2.1. Batch flotation test
The ore (1 kg, crushed to 2 mm during sampling) was ground
to 65% passing 76 lm in a closed stainless steel £240  90 mm
XMQ ball mill at a pulp density of 66% by weight. The bench-scale
flotation tests were performed in XFD-63 flotation cell (self aera-
tion) whose volume for rougher flotation was 3.0 dm3, for separa-
tion flotation of copper/iron sulfide minerals was 1.0 dm3, and for
copper or molybdenum cleaner flotation was 0.5 dm3, respectively.
After wet grinding, the pH of the pulp slurry was pre-adjusted
to any desired value by the addition of effective amounts of lime.
Then, effective amounts of collector or frother were added to the
slurry while agitating at about 1500 rpm and the slurry was condi-
tioned for a period of 3 min. At the end of the 3 min conditioning,
air was fed and the froth flotation was continued for about 4 min
during which a rougher concentrate was collected. The rougher
 G.-y. Liu et al. / Minerals Engineering xxx (2012) xxx–xxx 3

a Feed

Cu-Mo-Fe sulfide flotation Tailing 1

Rougher concentrate

Regrind

Cu/Fe separation Tailing 2 (Fe sulfide)

Cleaner concentrate

Mo/Cu separation Cu concentrate

Mo concentrate
b
Feed

Bulk-sulfide flotation Tailing 1

Frother or thiol collector flotation

Cu-Mo rougher concentrate Rougher concentrate

Cleaner flotation Middling Regrind

Cleaner concentrate 1 Tailing 2 (Fe sulfide)

Cu/Fe separation

Mo/Cu separation Cu concentrate

Cleaner concentrate 2

Mo concentrate
Mo/Cu separation Cu concentrate

Mo concentrate

c Feed

Non-thiol collector flotation Bulk-sulfide flotation Tailing 1

Cu-Mo rougher concentrate Rougher concentrate

Middling Desliming flotation Regrind

Mo/Cu preliminary separation Tailing 2 (Fe sulfide)

Cu/Fe separation

Cleaner concentrate 1 Cu middling

Cleaner concentrate 2

Mo/Cu separation Cu concentrate Mo/Cu separation Cu concentrate

Mo concentrate Mo concentrate

Fig. 1. The principle flowsheets for the recovery of Cu and Mo from a porphyry Cu–Mo ore. (a) Bulk flotation followed by separation. (b) Selective Cu flotation followed by
bulk flotation and then separation. (c) Preferential Mo flotation followed by Cu flotation.

concentrates and tailings were filtered, dried, weighted, sampled
and assayed for molybdenum and copper.
2.2.2. Industrial test
The industrial flotation was performed in the mineral process-
ing plant at the Dexing copper mine. The experimental system
M1 processed 8000 t/d, the control systems M2 and M3 processed
10,000 t/d and 20,000 t/d, respectively. The principle flotation flow
sheet of industrial and bench-scale tests was described in Fig. 1.
The experimental system used MC-103 as molybdenum collector
in the molybdenum circuit, and then the tailing of molybdenum
circuit was treated by a copper circuit using PECTU and SBX as col-
lectors. The control system used PECTU and SBX as collectors in the
rougher flotation.

Please cite this article in press as: Liu, G.-y., et al. A novel approach for preferential flotation recovery of molybdenite from a porphyry copper–molybde-
num ore. Miner. Eng. (2012), doi:10.1016/j.mineng.2012.02.008
4 G.-y. Liu et al. / Minerals Engineering xxx (2012) xxx–xxx

Table 1 flotation separation of molybdenite from copper sulfide minerals,

The head assay of ore samples used in the bench-scale flotation tests. thus increasing the consumption of Na2S. Therefore, we selected
Samples Head assay (%) Head assay Copper oxide diesel oil and DEP mixture with some additives as molybdenite col-
(g/t) ratio (%) lector to perform the sequent flotation tests, and named this mix-
Cu Mo S Fe Au Ag ture as MC-103.
Normal ore 0.422 0.0085 2.24 4.35 0.334 1.01 4.12
High-oxided ore 0.445 0.0077 1.21 4.07 0.286 0.95 13.26 3.2. Condition flotation tests

3.2.1. Effect of feed particle size distribution

Under the flotation condition of MC-103 64 g/t, and rougher pH
Table 2 7.5 for high-oxided ore and pH 9.0 for normal ore, the effects of the
The reagents used in the bench-scale flotation tests.
particle size distributions of rougher pulp slurry on the recoveries
Reagents Product Function and grades of copper and molybdenum in the Cu–Mo rougher con-
name centrates were shown in Fig. 5. It indicated that with the increase
Pine oil – Frother of the ratio of slurry particles passed 76 lm, the recoveries of Mo
C5-C8 alcohol mixture F-111 Frother and Cu increased and the grades of Mo and Cu slightly decreased.
Diethyl phthalate DEP Frother
When the distribution of particle sizes was over 65% minus 76 lm,
Kerosene – Non-thiol collector
Diesel oil – Non-thiol collector the increase of Mo recoveries became tardo. So, the feed particle
Diesel oil and diethyl phthalate MC-103 Non-thiol collector size distribution of 65% minus 76 lm was selected to perform
mixture the sequent flotation tests. Fig. 5 also shows that compared to
O-isopropyl-N-ethyl Z-200 Selective thiol collector the normal ore, the high-oxided ore could achieve superior Mo
thionocarbamate
N,N-dimethyl thionocarbamate AP Selective thiol collector
grades and recoveries with inferior Cu grades and recoveries in
mixture the Cu–Mo rougher concentrates.
O-isooctyl-N-ethoxycarbony IOECTC Selective thiol collector
thionocarbamate
3.2.2. Effect of collector dosage
N-propyl-N-ethoxycarbonyl PECTU Selective thiol collector
thiourea
Under the flotation condition of particle size distribution (65%
Sodium butyl xanthate SBX Thiol collector used in Cu 76 lm), and rougher pH 7.5 for high-oxided ore and pH 9.0 for
circuit normal ore, the influences of the dosage of MC-103 on the Mo
and Cu recoveries and grades in the Cu–Mo rougher concentrates
were shown in Fig. 6. It indicated that with the increase of the dos-
3. Results and discussion age of MC-103, the recoveries of Mo and Cu increased and the
grades of Mo and Cu decreased. When the dosage of MC-103 was
3.1. Exploratory flotation tests over 64 g/t, the increase of Mo and Cu recoveries turned smooth
for both normal ore and high-oxide ore. As a result, 64 g/t MC-
Using the high-oxided ore as the test samples, under rougher 103 was adopted in the following rougher operation.
pH 7.5 and feed particle size distribution of 65% minus 76 lm,
the flotation tests of collectorless, non-thiol collector and selective 3.2.3. Effect of rougher pH
thiol collector were carried out. The test results were listed in Figs. Under the flotation condition of particle size distribution (65%
2–4. Fig. 2 demonstrates that pine oil and C5–C8 alcohol Mixture 76 lm) and MC-103 (64 g/t), the effects of the rougher pH values
(F-111) got the similar flotation results for both copper and molyb- on the Mo and Cu recoveries and grades in the Cu–Mo rougher
denum, and compared to pine oil and F-111, diethyl phthalate concentrates were shown in Fig. 7. It indicated that with the in-
(DEP) obtained a superior Mo recovery in the Cu–Mo rougher con- crease of the rougher pH values, the Mo recoveries increased
centrate at a low dosage. Fig. 3 further indicates DEP got a higher slowly for both normal ore and high-oxided ore. While Mo grades
Mo recovery than F-111 when they were used with fuel oil, and and recoveries decreased at rougher pH > 9.0 for the normal ore
diesel oil obtained a higher Mo recovery than kerosene. Fig. 4 and pH > 9.5 for the high-oxided ore. Compared to 0.31% Mo grade
shows that compared to collectorless and non-thiol collector flota- and 90.2% Mo recovery at pH 9.5 for the high-oxided ore, the
tion, selective thiol collector flotation got a high Cu and Mo Mo grade and recovery at pH 7.5 were 0.35% and 89.2%, respec-
recoveries in the Cu–Mo rougher concentrate under using F-111 tively, which meant Mo recovery only increased 1% with losing
as a frother. However, compared to the combination of diesel oil 0.04% Mo grade and adding lime consumption. Therefore, the
and DEP, selective thiol collectors got a superior Cu recovery with recommended rougher pH values were 7.5 for the high-oxided
an inferior Mo recovery, which might increase the difficulty in ore and 9.0 for the normal ore.

(a) 80 1 (b) 80 40
Mo recoveries/%

70 0.8
Cu recoveries/%

60
Mo grades/%

Cu grades/%

30
60 0.6
40
50 0.4
20
20
40 0.2

30 0 0 10
1 2 3 4 5 6 1 2 3 4 5 6
Frother Frother

Fig. 2. The effects of frother on the recoveries and grades of Cu and Mo in the Cu–Mo rougher concentrates: 1 – pine oil 16 g/t, 2 – pine oil 24 g/t, 3 – F-111 16 g/t, 4 – F-111
24 g/t, 5 – F-111 8 g/t + DEP 8 g/t, 6 – DEP 16 g/t.

Please cite this article in press as: Liu, G.-y., et al. A novel approach for preferential flotation recovery of molybdenite from a porphyry copper–molybde-
num ore. Miner. Eng. (2012), doi:10.1016/j.mineng.2012.02.008
 G.-y. Liu et al. / Minerals Engineering xxx (2012) xxx–xxx 5

(a) 90 1
(b) 80 30

0.8
Mo recoveries/%

Cu recoveries/%
70 60 25

Mo grades/%

Cu grades/%
0.6
50 40 20
0.4
30 20 15
0.2

10 0 0 10
1 2 3 4 1 2 3 4
Fuel oil Fuel oil

Fig. 3. The effects of fuel oil on the recoveries and grades of Cu and Mo in the Cu–Mo rougher concentrates: 1 – kerosene 64 g/t + F-111 16 g/t, 2 – kerosene 64 g/t + DEP 16 g/
t, 3 – diesel oil 64 g/t + F-111 24 g/t, 4 – diesel oil 64 g/t + DEP 16 g/t.

(a) 90 1 (b) 80 30

80 0.8
Mo recoveries/%

Cu recoveries/%
60

Mo grades/%

Cu grades/%
20
70 0.6
40
60 0.4
10
20
50 0.2

40 0 0 0
1 2 3 4 1 2 3 4
Selective thiol collector Selective thiol collector

Fig. 4. The effects of selective thiol collector on the recoveries and grades of Cu and Mo in the Cu–Mo rougher concentrates: 1 – Z-200 8 g/t + F-111 16 g/t, 2 – IOECTC 6 g/
t + F-111 16 g/t, 3 – AP 8 g/t + F-111 16 g/t, 4 – PECTU 4 g/t + F-111 16 g/t.

(a) 90 1.0
(b) 90 30

84 0.8 75 25
Mo recoveries/%

Cu recoveries/%
Mo grades/%

Cu grades/%
60 20
78 0.6
45 15
72 0.4
30 10
66 0.2
15 5

60 0.0 0 0
60 62 64 66 68 70 60 62 64 66 68 70
The ratio of slurry particles passed 76µm/% The ratio of slurry particles passed 76µm/%

Fig. 5. The recoveries and grades of Cu and Mo in the Cu–Mo rougher concentrates as a function of feed particle size distribution: ( , j) – high-oxide ore, ( , N) – normal ore.

50
(a) 100 1.0 (b) 90

80
Cu recoveries/%

70 40
Mo recoveries/%

0.8
Mo grades/%

Cu grades/%

60
0.6 50 30
40

0.4 30 20
20

0 0.2 10 10
32 48 64 80 32 48 64 80
Dosage of MC-103 (g/t) Dosage of MC-103 (g/t)

Fig. 6. The effects of the dosage of MC-103 on the recoveries and grades Cu and Mo in the Cu–Mo rougher concentrates: ( , j) – high-oxide ore, ( , N) – normal ore.

3.2.4. Cleaner flotation test were obtained and used in situ to be cleaned. The purpose of these
Under the flotation condition of particle size distribution (65% cleaner flotation tests was to evaluate the influence of the dosage
76 lm) and MC-103 (64 g/t), rougher pH 7.5 for the high-oxided of Na2S on the preliminary separation of molybdenite from copper
ore and pH 9.0 for the normal ore, the Cu–Mo rougher concentrates sulfide minerals. After one blank cleaner flotation (desliming

Please cite this article in press as: Liu, G.-y., et al. A novel approach for preferential flotation recovery of molybdenite from a porphyry copper–molybde-
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6 G.-y. Liu et al. / Minerals Engineering xxx (2012) xxx–xxx

(a) 100 0.6

(b) 85 28

75 25
0.5

Cu recoveries/%
85
Mo recoveries/%

Cu grades/%
Mo grades/%
65 22

70 0.4 55 19

45 16
55 0.3
35 13

25 10
40 0.2 7.0 7.5 8.0 8.5 9.0 9.5 10.0
7.0 7.5 8.0 8.5 9.0 9.5 10.0
pH pH

Fig. 7. The effects of the rougher pH values on the recoveries and grades Cu and Mo in the Cu–Mo rougher concentrates: ( , j) – high-oxide ore, ( , N) – normal ore.

flotation), Na2S was added to depress copper sulfide minerals in
the second cleaner operation. The effects of the dosage of Na2S
on the Mo and Cu grades and recoveries were listed in Fig. 8. It
shown that with the increase of the dosage of Na2S, the Cu grades
and recoveries in the cleaner concentrate decreased markedly, and
the Mo recoveries decreased tardily and the Mo grades increased
significantly. When the dosage of Na2S was over 260 g/t for the
high-oxided ore and 300 g/t for the normal ore, the Mo grades in
the cleaner concentrate turned to decrease and the Mo recoveries
decreased fast. As a result, the suitable dosages of Na2S for the pre-
liminary separation of molybdenite from copper sulfide minerals
were 260–300 g/t.
3.3. Locked cycle tests
The locked cycle tests of preferential Mo flotation followed by
Cu flotation (Fig. 1c) were performed by using 64 g/t MC-103 and
260–300 g/t Na2S in the molybdenum circuit, 6 g/t PECTU and
20 g/t SBX in the copper circuit and pH 10.5 maintained by lime
in the Cu/Fe separation. For those of selective Cu flotation followed
by bulk flotation and separation (Fig. 1b), 10 g/t AP and 10 g/t F-
111 in the molybdenum circuit, 55 g/t SBX and 15 g/t F-111 in
the copper circuit and pH 13 maintained by lime in the Cu/Fe
separation were used (optimized reagent conditions by the mineral
processing plant). For those of bulk flotation followed by separa-
tion (Fig. 1a), 8 g/t PECTU, 20 g/t SBX and 20 g/t F-111 in the rough-
er circuit and pH 10.5 maintained by lime in the Cu/Fe separation
were adopted (Liu et al., 2011). The experimental results of these
locked cycle tests were shown in Tables 3 and 4.
Table 3 shows for the normal ore, the Mo grades and recoveries
in the cleaner concentrates were 0.367% and 60.15% for the bulk
flotation approach (Fig. 1a), 0.430% and 69.18% for the selective
Cu flotation approach (Fig. 1b), and 0.540% and 87.84% for the pref-
erential Mo flotation approach (Fig. 1c). Table 3 also indicates that
the bulk flotation approach only obtained 75.80% Mo recovery in
the rougher concentrate. The Mo recovery for the selective Cu flo-
tation approach was 61.79% in the cleaner concentrate 1 and
27.84% in the rougher concentrate. The Mo recovery for the prefer-
ential Mo flotation approach was 83.83% in the cleaner concentrate
1 and 9.09% in the rougher concentrate. Based on crude ore, the
loss of molybdenite from the rougher concentrate was 15.65% for
bulk flotation approach, 20.45% for selective Cu flotation approach
and only 5.08% for preferential Mo flotation approach during the
Cu/Fe flotation separation. These meant the new approach could

80 100 1.5
(a) 2.0
(b)
80 1.2
Mo recoveries/%
Mo recoveries/%

60 1.5
Mo grades/%
Mo grades/%

60 0.9
40 1.0
40 0.6
20 0.5
20 0.3

0 0.0 0 0.0
0 130 260 390 0 100 200 300 400
Dosage of Na 2S (g/t) Dosage of Na 2S (g/t)

50 50 60
(c) (d) 80

40 40
Cu recoveries/%

60 45
Cu recoveries/%

Cu grades/%
Cu grades/%

30 30
40 30
20 20
20 15
10 10

0 0 0 0
0 130 260 390 0 100 200 300 400
Dosage of Na 2S (g/t) Dosage of Na 2S (g/t)

Fig. 8. The effects of the dosage of Na2S used in the Mo/Cu preliminary separation operation on the recoveries and grades Cu and Mo in the cleaner concentrates: ( , j) –
high-oxide ore, ( , N) – normal ore.

Please cite this article in press as: Liu, G.-y., et al. A novel approach for preferential flotation recovery of molybdenite from a porphyry copper–molybde-
num ore. Miner. Eng. (2012), doi:10.1016/j.mineng.2012.02.008
 G.-y. Liu et al. / Minerals Engineering xxx (2012) xxx–xxx 7

Table 3
The locked cycle tests for the normal ore.

Approach Product Ratio, w (%) Grade (%) Recovery (%)

a
Cu Mo Au Cu Mo Au
Bulk flotation (Fig. 1a) Rougher concentrate 7.96 4.91 0.081 2.88 92.78 75.80 68.22
Cleaner concentrate 1.39 26.72 0.367 14.25 88.23 60.15 58.97
Selective Cu flotation (Fig. 1b) Cleaner concentrate 1 0.81 28.62 0.653 12.89 55.30 61.79 30.90
Rougher concentrate 6.69 2.32 0.036 1.82 36.98 27.84 35.97
Cleaner concentrate 1 + rougher concentrate 7.50 5.16 0.102 3.01 92.28 89.63 66.87
Cleaner concentrate 2 0.57 23.53 0.111 16.10 31.99 7.39 27.17
Cleaner concentrate 1 + 2 1.38 26.52 0.430 14.21 87.29 69.18 58.07
Preferential Mo flotation (Fig. 1c) Cleaner concentrate 1 0.59 25.92 1.221 11.78 36.33 83.83 20.73
Rougher concentrate 7.24 3.32 0.011 2.46 57.10 9.09 53.15
Cleaner concentrate 1 + rougher concentrate 7.83 5.02 0.102 3.16 93.43 92.92 73.88
Cleaner concentrate 2 0.82 27.46 0.042 16.93 53.49 4.01 41.41
Cleaner concentrate 1 + 2 1.41 26.82 0.540 14.78 89.82 87.84 62.14
a
Unit, g/t.

Table 4
The locked cycle tests for the high-oxided ore.

Approach Product Ratio, w (%) Grade (%) Grade (g/t) Recovery (%)
Cu Mo Au Ag Cu Mo Au Ag
Bulk flotation (Fig. 1a) Rougher concentrate 6.57 5.39 0.108 3.37 12.93 80.81 89.82 77.68 81.60
Cleaner concentrate 1.45 23.64 0.368 12.16 44.58 78.23 67.24 61.94 62.08
Preferential Mo flotation (Fig. 1c) Cleaner concentrate 1 0.50 25.15 1.312 14.35 42.12 29.20 83.46 25.24 22.17
Rougher concentrate 6.66 3.63 0.012 2.37 8.62 55.40 10.26 55.00 59.80
Cleaner concentrate 1 + rougher concentrate 7.16 5.13 0.103 3.21 10.96 84.60 93.72 80.24 81.97
Cleaner concentrate 2 0.92 24.96 0.041 13.59 46.40 52.68 4.72 43.44 44.39
Cleaner concentrate 1 + 2 1.42 25.03 0.492 13.86 44.88 81.88 88.18 68.68 66.56

dramatically reduce the influence of lime on the floatability of
molybdenite and shown an obvious superiority in improving the
Mo flotation recovery from its porphyry Cu–Mo ore. Table 3 further
demonstrates that compared to the bulk flotation and selective Cu
flotation approach, the preferential Mo flotation achieved superior
metallurgical performance in flotation recovery of other co-present
metal values such as gold.
Table 4 indicates the preferential Mo flotation approach ob-
tained 1.312% Mo with 83.46% Mo recovery in the cleaner concen-
trate 1 from the high-oxided ore (Fig. 1c), and the total Mo
recovery in the cleaner concentrate 1 and rougher concentrate (be-
fore Cu/Fe separation) reached 93.72%. While the bulk flotation ap-
proach obtained 0.368% Mo with 67.24% Mo recovery in the
cleaner concentrate (Fig. 1a), and the Mo recovery in the rougher
concentrate (before Cu/Fe separation) reached 89.82%. The differ-
ence of Mo recovery was only 3.90% before Cu/Fe separation, but
increased to 16.22% after Cu/Fe separation (the difference of Mo
recovery was 20.94% in the total cleaner concentrate). Therefore,
it was clear that the floatability of molybdenite was dramatically
impaired in the Cu/Fe separation and lime might play a crucial role
in depression of pyrite and molybdenite (Chander and Fuerstenau,
1972; Raghavan and Hsu, 1984; Liu et al., 2011). Table 4 also shows
that the new approach achieved better metallurgical performance
tained 0.655% Mo with 88.49% Mo recovery in the molybdenum
circuit, and the differential values D of molybdenum grade and
recovery between experimental system M1 and control systems
M2 and M3 (i.e., D = M1 M2, or M1 M3) were obvious. Com-
pared to the control systems M2 and M3 with the bulk flotation ap-
proach, the experimental system M1 with the preferential Mo
flotation approach returned superior performance with an increas-
ing recovery and grade of molybdenum by over 34.0% and 0.4%,
respectively. Moreover, the preferential Mo flotation approach also
achieved superior metallurgical performance in flotation recovery
of other co-present metal values during the industrial flotation
tests.
3.5. Mo/Cu flotation separation
The cleaner concentrate 1 of the industrial flotation tests was
adopted to evaluate the floatability of molybdenite. The selected
cleaner concentrate 1 with 0.632% Mo and 26.77% Cu collected
from a day shift was used in the locked cycle tests. The flotation
experiments were carried out under the reagent conditions such
100
Mo recoveries/%

in flotation recovery of other co-present metal values such as gold 80

and silver than the bulk flotation approach, even the Mo recovery
60
was higher than Cu recovery in the overall cleaner concentrates.
40
3.4. Industrial tests
20

The Mo recoveries of the cleaner concentrate 1 of every indus- 0

0 5 10 15 20 25 30
trial-flotation-test shift were shown in Fig. 9, and the Mo statistical
Shift
results of the continuous operation 30 shifts were listed in Table 5.
It was evident from the results in Table 5 that the preferential Mo Fig. 9. The Mo recoveries of the cleaner concentrate 1 in every industrial-flotation-
flotation approach returned an excellent cleaner concentrate con- test shift.

Please cite this article in press as: Liu, G.-y., et al. A novel approach for preferential flotation recovery of molybdenite from a porphyry copper–molybde-
num ore. Miner. Eng. (2012), doi:10.1016/j.mineng.2012.02.008
8 G.-y. Liu et al. / Minerals Engineering xxx (2012) xxx–xxx
Table 5
The Mo flotation results of industrial tests.
System Feed (%) Cleaner concentratea (%)
Mo grade Mo grade
M1 (experiment) 0.0056 0.655
M2 (control) 0.0055 0.199
M3 (control) 0.0054 0.214
a
The cleaner concentrate for M1 was cleaner concentrate 1 (Fig. 1c).
Table 6
The locked cycle results of the Mo/Cu flotation separation.
Product Ratio, w (%) Grade (%) Recovery (%)
Mo Cu Mo
Mo concentrate 1.17 48.83 0.83 90.60
Cu concentrate 98.83 0.06 27.08 9.40
Cleaner concentrate 1 100.00 0.631 26.77 100.00
as overall 18.5 Kg/t Na2S, 1.2 Kg/t water glass and 130 g/t kerosene,
and under the operation sequences as one rougher flotation and
one cleaner flotation, then regrinding the obtained cleaner concen-
trate to over 95% minus 76 lm, following four cleaner operations.
Within the cleaner section, the tail of each cleaner stage except the
first was returned to the head of the previous cleaning stage. The
locked cycle result of the Mo/Cu separation tests was listed in Ta-
ble 6. It indicated that the Mo grade and recovery in the Mo con-
centrate were 48.83% and 90.60%, respectively, and the Cu grade
was only 0.83%. While the Mo grade and recovery were commonly
40–45% and 70–80% for the Mo/Cu flotation separation of the clea-
ner concentrate produced by bulk flotation or selective Cu flotation
of Dexing porphyry Cu–Mo ore, and the consumption of Na2S was
35–45 kg/t. These meant the preferential Mo flotation approach
could obtain a relatively high grade of molybdenite in the cleaner
concentrate 1 uncontaminated with thiol collectors, and could eas-
ily performed the Mo/Cu flotation separation under low consump-
tion of Na2S. As a result, the preferential Mo flotation approach
using the MC-103 collector in the molybdenum circuit could ob-
tain superior Mo grade and recovery not only in the Mo–Cu recov-
ery stage, but also in the Mo/Cu separation stage, could increased
Mo flotation recovery by 20–40% as well as saved about ½ Na2S
consumption from Dexing porphyry Cu–Mo ore.
4. Conclusions
In this paper, a preferential Mo flotation approach was investi-
gated to concentrate molybdenite from Dexing porphyry Cu–Mo
ore through bench-scale and industrial flotation tests. The flotation
tests involved in the systematic evaluation of flotation reagents,
ore kinds, flotation flowsheets, particle size distributions, flotation
pH values and Na2S dosages on the influence of molybdenite recov-
ery. Based on the recommended conditions, the locked cycle tests
and industrial tests were carried out.
(1) The locked cycle flotation results of both normal ore and high-
oxided ore indicated that compared with the bulk flotation
and selective Cu flotation approach, the preferential Mo flota-
tion approach using a new non-thiol collector MC-103 could
obtain a superior cleaner concentrate with high Mo recovery
and grade in the molybdenum circuit. While the molybde-
num circuit tailing was treated by a copper flotation circuit
to obtain a high recovery of other co-present metal values.
(2) The industrial flotation results demonstrated that the prefer-
ential Mo flotation approach obtained an excellent cleaner
concentrate contained 0.655% Mo with 88.49% Mo recovery
Please cite this article in press as: Liu, G.-y., et al. A novel approach for preferential flotation recovery of molybdenite from a porphyry copper–molybde-
num ore. Miner. Eng. (2012), doi:10.1016/j.mineng.2012.02.008
Dgrade (Mo) Mo recovery Drecovery (Mo)
– 88.49 –
+0.465 50.66 +37.83
+0.441 53.77 +34.72
in the molybdenum circuit. Compared with the bulk flotation
approach, the preferential Mo flotation approach increased
the Mo recovery and grade over 34.0% and 0.4%, respectively.
(3) For being uncontaminated with thiol collectors, this cleaner
Cu
concentrate was readily treated by flotation to separate
0.04 molybdenite from copper sulfide minerals under a low con-
99.96
sumption of Na2S. As a whole, the preferential Mo flotation
100.00
approach followed by Mo/Cu flotation separation, increased
Mo recovery by 20–40% in the final Mo concentrate (with
>45% Mo) as well as saved about ½ Na2S consumption during
flotation recovery of molybdenum from Dexing porphyry Cu–
Mo ore.
Acknowledgements
The authors would like to thank the National Natural Science
Foundation of China (51074183 and 50604016), the Foundation
for the Author of National Excellent Doctoral Dissertation of China
(2007B52), the Program for New Century Excellent Talents in Chi-
nese University (NCET-08-0568), and the National Science and
Technology Support Project of China (2007BAB22B01) for the
financial support of this research. We would particularly acknowl-
edge Dexing Copper Mine and Jiangxi Copper Corporation for pro-
viding financial support and convenient help.
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