J. Cent. South Univ. Technol.

(2009) 16: 0753−0757

DOI: 10.1007/s11771−009−0125−0

Effect of organic depressant lignosulfonate calcium on separation of

chalcopyrite from pyrite

LIU Run-qing(刘润清), SUN Wei(孙 伟), HU Yue-hua(胡岳华), WANG Dian-zuo(王淀佐)

(School of Resources Processing and Bioengineering, Central South University, Changsha 410083, China)

Abstract: In order to selectively separate chalcopyrite from pyrite，the effect of organic depressant lignosulfonate calcium (LSC) on
the flotation separation of chalcopyrite from pyrite was investigated by flotation tests. The depression mechanism was studied by
Fourier-transform-infrared (FTIR) analysis. The flotation tests of single mineral show that LSC can depress the flotation of pyrite in a
certain pH range, but it has little effect on chalcopyrite flotation. Flotation separation of a mixture of chalcopyrite and pyrite can be
completed to obtain a copper concentrate grade up to 24.73% with a recovery of 80.36%. IR analysis shows that LSC and butyl
xanthate compete in absorption on pyrite surface, and there exists an LSC characteristic peak on pyrite surface. There is little
adsorption of LSC on chalcopyrite.

Key words: flotation; chalcopyrite; pyrite; depression; separation

sulphite, hydroxide, calcic compounds, or a combination

1 Introduction
Pyrite is the most widespread and abundant of
naturally occurring metal sulfide, which is often
associated with other valuable metal sulfides such as
chalcopyrite, galena and sphalerite [1−2]. Hence,
separation of pyrite from other associated metal sulfides
is desirable for the economical extraction of these
valuable metals. Because pyrite has good electric
conductivity and similar floatability with chalcopyrite,
the separation of chalcopyrite from pyrite becomes
difficult, and also pyrite misreports into the copper
concentrate because of its accidental activation by copper
released from chalcopyrite during grinding or
conditioning [3−7].
During the past years, many researches on the
separation of chalcopyrite from pyrite have been carried
out. CHEN and FENG [8] studied the effect of CTP on
flotation separation of chalcopyrite and pyrite, and the
results showed that CTP could effectively separate pyrite
and chalcopyrite at pH 9 with CaO as adjusting reagent.
XIONG et al [9] investigated the effect of calcium
containing compounds on the flotation behavior of
chalcopyrite and pyrite. But their study is restricted to
high pH values, long conditioning time and extensive
surface oxidation to realize the depressing of pyrite
flotation. Most of the reagents are inorganics, such as
cyanides, polymers, ferrocyanides, zinc sulphate,
of these reagents [10−13]. Of all depressants, cyanides
and lime are the most common. However, cyanides have
raised concern on environment [14]. Lime is apt to form
the dirt and jam the pipeline. Hence, natural, bio-
degradable, and non-toxic reagents receive importance
and held promise to function as a selective depressant
[15−16].
LSC is derived from the paper pulp waste liquor by
simple treatment. The relative molecular mass of LSC is
1 000−20 000. Its molecule includes hydroxyl group
(—OH) and sulfonic group (—SO3H). LSC, as a flotation
depressant, both in the laboratory and in commercial
processes, has been reported [17]. LSC has ever been
used to depress the calcite and barite, but it has seldom
been reported to be used as depressant of sulfides.
In this work, the effect of LSC on flotation behavior
of pyrite and chalcopyrite in the butyl xanthate (BX)
system was investigated, and the flotation separation of
chalcopyrite and pyrite was conducted in the mixed
mineral system. FTIR was also used to explain the
flotation results and investigate the adsorption
mechanism of LSC on pyrite surface.
2 Experimental
2.1 Samples and reagents
Pure handpicked mineral samples of pyrite and
chalcopyrite were obtained respectively from Tongling

Foundation item: Project(2006AA06Z120) supported by High-Technology Research and Development Program of China; Project(1343-74334000028)
supported by the Graduate Student Education Innovation Project of Central South University, China
Received date: 2008−11−07; Accepted date: 2009−02−24
Corresponding author: HU Yue-hua, Professor; Tel: +86−731−88879815; E-mail: HYH@mail.csu.edu.cn
754
mine of Anhui Province and Chenzhou of Hunan
Province. The mineral samples were crushed,
handpicked and dry-ground with a porcelain ball mill
and dry-sieved to obtain different size fractions. The
fraction less than 106 µm was used for flotation studies.
The fraction less than 37 µm was used for FTIR studies.
The minerals were stored in a desiccator under nitrogen
atmosphere. The purity of the mineral samples was
ascertained by mineralogical studies. Chemical analysis
of two mineral samples indicated that pyrite purity was
87.56% and chalcopyrite purity was 72.65%.
The collector was butyl xanthate, which was
industrial grade product from Chemical Factory of
Zhuzhou, China. 2# oil was employed as a frother, which
was also industrial grade product. HCl and NaOH were
adopted to adjust the pulp pH value, and organic
depressant LSC is a kind of chemical product.
2.2 Flotation test
In the flotation test, flotation machine of hitch
groove of XFG−1600 type with volume of 40 mL was
used. In each test, 2.0 g of sample was taken, then the
surface was cleaned for 10 min by using supersonic
cleaner in order to clean the oxide. The upper layer liquid
was settled and decanted, and then flushed in groove of
40 mL and pH value was adjusted. Depressant, collector
and frother were added by order. The conditioning time
for the depressant, collector and frother was 3, 2 and
1 min, respectively. The flotation was performed for 4 min.
The floating and non-floating fractions were filtrated,
dried and weighed for the recovery calculation.
The 40 mL groove was used in flotation separation
test of mixture minerals, 1.5 g chalcopyrite and 1.5 g
pyrite were taken, and the surface was cleaned by using
supersonic cleaner, respectively. Then they were mixed
to float. Products were filtrated, dried and weighed for
assessing the recovery by chemical analysis.
2.3 Infrared spectrum analysis
1.0 g sample was immersed in 25 mL solutions
containing corresponding reagent, ground for 30 min in
an agate mortar, settled for 30 min, and filtrated. The
solid obtained was dried under vacuum. Infrared spectra
were recorded in an NEXUS−470 infrared spectrum
apparatus.
3 Results and discussion
3.1 Effect of pH on flotation of chalcopyrite and pyrite
In order to selectively separate chalcopyrite from
pyrite, the effect of LSC on flotation of chalcopyrite and
pyrite at various pH values was studied. The results are
J. Cent. South Univ. Technol. (2009) 16: 0753−0757
shown in Fig.1. In the flotation test, the concentration of
LSC is 100 mg/L, butyl xanthate concentration is
0.1 mmol/L, and 2# oil concentration is 10 mg/L.
Fig.1 shows that both chalcopyrite and pyrite have
good floatability in wide pH region with butyl xanthate
as a collector and the recovery is more than 70%. At
pH＞10, pyrite recovery drops because pyrite surface
oxidation form hydroxyl compound, resulting in
hydrophilic surface in high pH. It can be seen that it may
be difficult to separate chalcopyrite from pyrite in
absence of depressant. Fig.1 also shows that depressant
LSC has good depression action on pyrite flotation in
whole pH range with butyl xanthate as a collector, while
LSC has no or little effect on chalcopyrite flotation.
According to the above results it can be inferred that the
flotation separation of pyrite from chalcopyrite may be
possible in wide pH range by using LSC as a depressant.
Fig.1 Effect of pH on flotation recovery of chalcopyrite and
pyrite (c(BX)=0.1 mmol/L; ρ(LSC)=100 mg/L; ρ(2# oil)=
10 mg/L)
3.2 Effect of LSC concentration on flotation of
chalcopyrite and pyrite
Effect of LSC concentration on the mineral
floatability was investigated at pH 6 and butyl xanthate
concentration of 0.1 mmol/L. The results are shown in
Fig.2. It follows that pyrite recovery sharply decreases
with the increase of LSC concentration. When LSC
concentration is 150 mg/L, pyrite recovery is 10.17%,
showing strong depression effect on the pyrite. However,
LSC has weak effect on chalcopyrite flotation. This
demonstrates the selective function of LSC on pyrite.
3.3 Separation of mixture mineral
On the basis of single mineral flotation test,
adopting sodium hydroxide to adjust pulp, the separation
test of manual mixed mineral was performed under the
condition of pH=9−10, LSC concentration of 150 mg/L,
J. Cent. South Univ. Technol. (2009) 16: 0753−0757 755
butyl xanthate concentration of 0.1 mmol/L, 2# oil
concentration of 15 mg/L. The results are listed in Table
1. From Table 1, it can be seen that LSC can effectively
separate pyrite from chalcopyrite with grade of copper
concentrate up to 24.73% with the recovery of 80.36%.
From the results it is indicated that the separation of
chalcopyrite and pyrite is possible in alkaline condition
with LSC as a depressant and butyl xanthate as a
collector.

Fig.3 FTIR spectrum of LSC

Fig.2 Effect of LSC concentration on flotation recovery of

chalcopyrite and pyrite (pH=5.9−6.1; c(BX)=0.1 mmol/L;
ρ(2# oil)=10 mg/L)

Table 1 Results of flotation separation of chalcopyrite-pyrite

manual mixture mineral
Fig.4 FTIR spectra of pyrite in presence and absence of
Recovery/ Grade/% Recovery/%
Product reagents: (a) Pyrite; (b) Pyrite +BX; (c) Pyrite +LSC+BX
% Cu S Cu S
Concentrate 47.80 24.73 36.87 80.36 43.07 1 096.2, 1 033.0 and 916.7 cm−1. As reported in Ref.[18],
Tailings 52.20 5.54 44.62 19.64 56.93 pyrite interacts with xanthate to form dixanthogen and
the characteristic peaks of dixanthogen appear at 1 269
Feed 100.00 14.71 40.92 100.00 100.00
and 1 024 cm−1. By analyzing Fig.4(b) in wavenumber
range of 1 000−1 300 cm−1, it can be found that there are
3.4 Mechanism of mineral-LSC interaction
adsorption peaks at 1 266.0 and 1 033.6 cm−1 on pyrite
The FTIR spectrum of LSC presented in Fig.3
surface, which indicates that there is dixanthogen
shows peaks at 2 936.9 and 1 415.9 cm−1 due to
formation on pyrite surface. Fig.4(c) shows that there are
stretching vibration and in-plane bending vibration of
adsorption of phenyl and C—S stretching vibration at
alkyl, and peaks at 1 114.2 and 1 078.2 cm −1
3 730.4, 1 594.0 and 636.7 cm−1. Also there are butyl
corresponding to asymmetry and symmetry vibration of
—SO3 group adsorption, respectively. The adsorption xanthate characteristic peaks at 2 965, 1 464 and 1 092
band of 619.4 cm−1 is corresponding to C—S stretching cm−1. This indicates that LSC and butyl xanthate are
vibration. Peaks at 1 663.7 and 1 355.6 cm −1 correspond adsorbed simultaneously on pyrite surface, but LSC
to stretching vibration of —COO− and —OH, and peaks carries numerous hydrophilic groups, which make the
at 1 587.2 and 1 514.4 cm −1 correspond to the pyrite surface hydrophilic and hence depress the flotation
characteristic adsorption of phenyl. The results indicate of pyrite.
that there are a number of function groups such as Fig.5 shows the FTIR spectra of chalcopyrite in
—COO−, —SO3 and —OH in the molecule of LSC. solution of butyl xanthate and LSC. It can be seen from
The FTIR spectra of different samples are shown in Fig.5(b) that the adsorption of butyl xanthate on
Fig.4. Fig.4(b) shows that there are obvious chalcopyrite occurs at 1 022.5 cm−1, showing the
characteristic peaks at 2 963.6, 1 467.1, 1 372.2, 1 266.0, formation of dixanthogen. Fig.5(c) shows that there is no
756
obvious absorption of LSC. This indicates that there is
no or little adsorption of LSC on chalcopyrite. This also
indicates that butyl xanthate is absorbed on the
chalcopyrite surface prior to LSC. The existence of LSC
cannot prevent butyl xanthate from being adsorbed on
chalcopyrite surface, so LSC has litter influence on the
chalcopyrite flotation.
Fig.5 FTIR spectra of chalcopyrite in presence and absence of
reagents: (a) Chalcopyrite; (b) Chalcopyrite+BX; (c) Chal-
copyrite+LSC+BX
Different mechanisms of LSC interaction with
chalcopyrite and pyrite were caused by different mineral
surface atomic structures and different chemical
properties. For pyrite, the existence of oxygen makes its
surface oxidized in the pulp by the reaction:
FeS2+11H2O−15e=Fe(OH)3+2SO42−+19H+
O2+4e+4H+=2H2O
After adding depressant LSC, oxidized product
Fe(OH)3 interacts with —SO3 of LSC. LSC is covered
on the pyrite surface, resulting in the reduction
atmosphere of pyrite surface, suppressing oxidization of
xanthate on the pyrite surface, and preventing the
formation of dixanthogen to reduce the pyrite flotation.
For the chalcopyrite, oxidation-reduction reactions
are as follows:
2CuFeS2+6H2O+6O2=2Fe(OH)3+Cu2S+3SO42−+6H+(3)
Cu2S+2X−=2CuX+S2−
When xanthate interacts with chalcopyrite, cuprous
or copper xanthogenate forms on chalcopyrite surface,
which is adsorbed on the chalcopyrite surface and makes
chalcopyrite hydrophobic. After adding depressant LSC,
though the chalcopyrite surface has iron ion, the
solubility of xanthogenate copper is very small. The
reaction between copper and xanthate ions is faster than
that between iron and sulfonic ions. The formation of
J. Cent. South Univ. Technol. (2009) 16: 0753−0757
xanthogenate on chalcopyrite surface hinders the contact
of sulfonic and iron ions. Therefore, LSC has weak
function on chalcopyrite. It may be the reason why LSC
could selectively depress pyrite in flotation separation
chalcopyrite and pyrite.
4 Conclusions
(1) Flotation tests show that LSC has good
depression action on pyrite flotation in whole pH range
with butyl xanthate as collector, while LSC has no or
little effect on chalcopyrite flotation. LSC can effectively
separate pyrite from chalcopyrite in wide pH range.
(2) The separation test of manual mixed mineral
shows that LSC can separate pyrite from chalcopyrite at
pH 9−10 with grade of copper concentrate up to 24.73%
and recovery of 80.36%.
(3) FTIR spectrum indicates that LSC has a number
function groups —OH and —SO3. Pyrite interacts with
xanthate and LSC, and LSC is covered on the pyrite
surface, and preventing the formation of dixanthogen on
pyrite surface, which makes the pyrite surface
hydrophilic, resulting in depressing the flotation. For
chalcopyrite, the reaction between copper ion and
xanthate ion is faster than that between iron ion and LSC,
so LSC has no or little adsorption of LSC on
chalcopyrite. The conclusion is in accordance with the
flotation results.
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