Minerals Engineering 19 (2006) 13801384

This article is also available online at:

www.elsevier.com/locate/mineng
Technical note

The separation of Cu/Fe sulde minerals at slightly alkaline

conditions by using ethoxycarbonyl thionocarbamates as
collectors: Theory and practice
Liu Guang-yi *, Zhong Hong, Dai Tai-Gen
Institute of Chemistry and Chemical Engineering, Central South University, 410083 Changsha, Hunan Province, PR China

Received 27 September 2005; accepted 14 December 2005

Available online 3 February 2006

Abstract

The bench-scale and industrial otation test results of Jiangxi Copper Corporation Yongping Copper Mine showed that the otation
separation of Cu/Fe sulde minerals has been achieved at pH values above 13 for xanthates, about 11 for dialkyl thionocarbamates and
around 8.5 for ethoxycarbonyl thionocarbamates (ECTC), respectively, and ECTC collectors were powerful for copper minerals and
very selective against iron sulde minerals at pH 89. The otation results have been explained from the structurereactivity relationship
of collectors by generalized perturbation theory and density functional calculation at B3PW91/6-31G(D) level.
 2005 Elsevier Ltd. All rights reserved.

Keywords: Non-ferrous metallic ores; Sulde ores; Flotation collectors; Mineral processing

1. Introduction line and neutral pH conditions (Fairthorne et al., 1996, 1997;

Xanthates interact with the majority of sulde minerals to
form metal xanthate and dixanthogen, therefore the selectiv-
ity is low without the use of additional reagents. For exam-
ple, the otation separation of copper sulde minerals from
iron sulde minerals is only achieved at high pH values. This
not only consumes a large amount of lime and increases the
plant operating cost but also depresses the otation of some
copper minerals (Nagaraj et al., 1986, 1988). Dialkyl thio-
nocarbamates are powerful collectors for the otation of
copper sulde minerals and are more selective than xanth-
ates against pyrite at mildly alkaline pH values (Seryakova
et al., 1975; Woods and Hope, 1999; Liu, 2004). Recently,
new otation collectors ethoxycarbonyl thionocarbamates
(ECTC) with a high specicity for copper minerals and pre-
cious metals have been developed by Cytec Industries Inc. A
previous study has shown that ECTC collectors were power-
ful for chalcopyrite and very selective against pyrite in alka-
Shen et al., 1998; Fu et al., 1986; Fu and Wang, 1989; Boul-
ton et al., 2000; Nagaraj et al., 1988; Nagaraj and Brinen,
1996, 2001; Basilio, 1989; Mielczarski and Yoon, 1991).
Whereas, theoretical investigation on the structurereactiv-
ity relationship of ECTC collectors is not involved in the
previous study and ECTC used as a single collector for the
preferential otation of copper sulde minerals from iron
sulde minerals in practice has not been reported. In this
study, we will compare the collecting performance of eth-
oxycarbonyl thionocarbamates with dialkyl thionocarba-
mates and xanthates not only in the otation of copper
sulde minerals from iron sulde minerals in Yongping
Copper Mine, but also from their structurereactivity rela-
tionship by generalized perturbation theory and density
functional calculation at B3PW91/6-31G(D) level.
2. Experimental section
2.1. Flotation tests

*
Corresponding author. Tel.: +86 731 8836309; fax: +86 731 8879616. The test material was ore from Yongping Copper Mine
E-mail address: guangyi.liu@163.com (G.-y. Liu). of Jiangxi Copper Corporation in China, and the main

0892-6875/$ - see front matter  2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2005.12.007
 G.-y. Liu et al. / Minerals Engineering 19 (2006) 13801384 1381

copper bearing minerals were chalcopyrite, chalcocite, 2.2. Computational methods

covellite and bornite and the main iron bearing minerals
were pyrite and marcasite and signicant amounts of
non-sulde gangue minerals were quartz, kaolinite, garnet
and calcite. Sodium butyl xanthate, Z-200 (O-isopropyl-
N-ethyl thionocarbamate) and IOECTC (O-isooctyl-N-eth-
oxycarbonyl thionocarbamate) used in this study were of
commercial grade. The ore (1 kg, crushed to 2 mm during
sampling) was ground to 65% passing 76 lm to liberate
90% copper sulde minerals in a closed steel
XMBU200 400 mm mill at a pulp density of 66% by
weight. The bench-scale otation tests were performed in
XFD-63 otation cell whose volume for rougher otation
was 3.0 dm3, for separation otation of copper/iron sulde
minerals was 1.0 dm3 and for cleaner otation was 0.5 dm3,
respectively.
The industrial otation was performed in the Mineral
Processing Plant of Yongping Copper Mine. The experi-
mental system processed 5000 t/d and the operating pH
for copper rougher and cleaner was 8.5 and, for iron sulde
mineral rougher was 7.0. The collector compared was
sodium butyl xanthate.
The otation owsheet of bench-scale and industrial
tests are described in Fig. 1. The bulk otation technique
by using sodium butyl xanthate as collector was set forth
in Fig. 1(a). The preferential otation technique by using
Z-200 or IOECTC as collector was set forth in Fig. 1(b),
but the copper cleaner pH for Z-200 technique was about
11.
All calculations were made using the Gaussian98 (Frisch
et al., 1998) and Chemoce 6.0 program and the energies
were corrected by means of the full counterpoise technique.
The initially molecular modeling of butyl xanthate ion, Z-
200 and IOECTC were optimized by MM2 and MP3 meth-
ods. The obtained geometries have been further optimized
at the HF/3-21G(D) level. The calculations for optimized
structures were made with DFT methods at the B3PW91/
6-31G(D) level.
3. Results and discussion
3.1. Flotation test
The bench-scale otation results for dierent collectors
at dierent cleaner pHs are shown in Fig. 2. It indicated
that the optimized cleaner pHs for otation separation of
copper/iron sulde minerals were above 13 for sodium
butyl xanthates, about 11 for Z-200 and around 8.5 for
IOECTC, respectively, and IOECTC collector showed
superior performance compared with sodium butyl xan-
thate and Z-200, both in terms of copper recovery and
grade in copper concentrates.
Because of the high specicity for copper minerals,
IOECTC was selected as copper collector in the industrial
tests performed in the Mineral Processing Plant of Yong-
ping Copper Mine. The statistical results obtained in a

Feed Feed

Lime 1400, pH 7.5 grinding Lime 1800, pH 8.5 grinding

classification classification
-0.074 mm 65% -0.074 mm 65%
collector collector
frother rougher frother
Copper rougher
Lime 900 collector
collector pH 8.5
pH 13
separation Clean. Scav.
frother
Lime 400 pH 8.5 collector
Scav.
pH 13 cleaner Clean. Scav.
Scav.
Lime 300
pH 13 cleaner Acidic water
collector
Sulfur rougher frother

Copper conc. Sulfur conc. Tailings Copper conc. Sulfur conc. Tailings

(a) Bulk flotation followed by separation (b) Preferential flotation of copper

by using sodium butyl xanthate as sulfide minerals by using IOECTC or
collector Z-200 as collector
Fig. 1. Flowsheet of the closed circuit otation tests.
1382 G.-y. Liu et al. / Minerals Engineering 19 (2006) 13801384

90 net charge at the reactive center of otation reagent or min-

80 Copper recovery eral, and the energy of normal covalent bond was involved
70 in electron-donating power of reagents and electron-
60 accepting power of minerals, and the energy of back dona-
%

50 tion covalent bond was involved in electron-back-donating

40
30 Copper grade
20
10
7 8 9 10 11 12 13 14
pH
Fig. 2. Copper recovery and copper grade in copper concentrate as a
function of cleaner pH values in the closed circuit otation tests, otation
conditions: (j)IOECTC, copper rougher: IOECTC 8 g/t, copper
scavenger: IOECTC 4 g/t, (m)Z-200, copper rougher: Z-200 12 g/t,
pine oil 5 g/t, copper scavenger: Z-200 4 g/t, ()sodium butyl xanthate
(SBX), rougher: SBX 40 g/t, pine oil 15 g/t, scavenger: SBX 20 g/t, pine oil
10 g/t.
month of industrial tests and the adopted reagent condi-
tions are described in Table 1. It is evident from the results
in Table 1 that IOECTC collector returned superior metal-
lurgy at pH 8.5 compared with sodium butyl xanthate at
pH 13. Compared with bulk otation followed by separa-
tion by using sodium butyl xanthate as collector, the pref-
erential otation of copper minerals by using IOECTC as
collector increased copper grade 0.71%, and recoveries of
copper 3.01%, gold 8.33% and silver 9.08% in copper con-
centrates, respectively.
It is evident from the results of industrial tests that
ECTC collectors were powerful for copper minerals and
very selective against iron sulde minerals at pH 89 and
the recoveries and grades of copper, silver and gold in
the copper concentrates were very eective.
3.2. Quantum chemistry calculation
Generalized perturbation theory (Klopman, 1968; Wang
et al., 1996) indicated that the interaction between otation
reagents and minerals was composed of electrostatic eect,
normal covalent bond and back donation covalent bond.
The energy of electrostatic eect was proportional to the
power of minerals and electron-accepting power of
reagents.
The copper having (t2g)6(eg)3Cu(k) or t6e4Cu(j) congu-
ration on the surfaces of copper sulde minerals can accept
frontier electron of collectors to form a r-bond, also easily
donate its richly d-orbital electron (feedback electron) to
the frontier orbital of collector resulting in the formation
of a dative p-bond. While the iron having (t2g)6Fe(k) and
3 2
ta2g eag Fejjj conguration Fejjj is the predominant
composition at alkaline conditions) on the surfaces of iron
sulde minerals interacts chemically with collectors basi-
cally through accepting frontier electron of collectors to
form a r-bond.
Table 2 shows that the value of net charge of sulfur
atom was followed as this sequence: IOECTC > Z-
200 > butyl xanthate ion. Accordingly, based on the elec-
trostatic eect and normal covalent bond of generalized
perturbation theory, the selectivity of these collectors
against iron sulde minerals would be followed in the order
of IOECTC > Z-200 > butyl xanthate ion and their collect-
ing power for copper sulde minerals was followed in the
order of IOECTC < Z-200 < butyl xanthate ion.
Table 2 also demonstrates the highest occupied molecu-
lar orbits (HOMO) of butyl xanthate ion, Z-200 and
IOECTC which were composed by p-orbits of sulfur atoms
in each collector molecule, which inferred that sulfur atom
was of the reactive center of these collectors and could
donate its frontier electron to metal cation on the mineral
surface resulted in the formation of r-bond. The orbital
eigenvalues and compositions of lowest unoccupied molec-
ular orbits (LUMO) of these collectors indicated that three
collectors had the power of overlapping of d-orbits of
metal cation with their LUMO to form dative p-bond.
The HOMO eigenvalue of butyl xanthate ion was
0.03129 a.u., higher than those of Z-200 and IOECTC.
Butyl xanthate ion was easier to donate its frontier electron

Table 1
The conditions and results of the industrial experiments
System Dosage of reagent (g/t) Products Ratio (%) Grade (%) Recovery (%)
Cu S Aua Aga Cu S Au Ag
IOECTC Copper rough.: IOECTC 8 Copper conc. 2.492 23.81 28.49 0.578 167.37 87.99 6.77 34.13 58.28
Copper scav.: IOECTC 4 Sulfur conc. 12.004 0.219 42.64 0.089 11.105 3.90 48.81 25.32 18.63
Cleaner: pH 8.5 Tailings 85.504 0.064 5.45 0.02 1.932 8.11 44.42 40.55 23.09
Sulfur rough.: SBX 60, Feed 100.0 0.674 10.49 0.042 7.156 100.0 100.0 100.0 100.0
pine oil 20
Sodium butyl Rough.: SBX 50, Copper conc. 2.428 23.10 28.90 0.49 162.4 84.98 6.77 25.80 49.20
xanthate pine oil 20 Sulfur conc. 16.703 0.285 41.42 0.108 14.268 7.21 66.77 39.12 29.74
Scav.: SBX 20, Tailings 80.869 0.064 3.39 0.02 2.087 7.81 26.46 35.08 21.06
pine oil 5 Feed 100.0 0.660 10.36 0.046 8.014 100.0 100.0 100.0 100.0
Cleaner: pH 13
a
g/t.
 G.-y. Liu et al. / Minerals Engineering 19 (2006) 13801384
Table 2
The net charge of sulfur and frontier orbital eigenvalues and compositions of collectors at B3PW91/6-31G(D) level
Collectors Net charge HOMO
of sulfur
Eigenvalues/a.u. Molecular orbital
compositions
Butyl xanthate 0.3466, 0.03129 pz-orbit of S atoms
ion 0.2952 in C(@S)S group
Z-200 0.3203 0.20686 px-orbit of S atom
in C@S group
IOECTC 0.1811 0.21642 px- and py-orbits of S
atom in C@S group
to metal cation on the mineral surfaces to form normal
covalent bond. At the same time, the LUMO of butyl xan-
thate ion could overlap the d-orbits of metal cation on the
mineral surface to form back donation covalent bond.
Butyl xanthate ion would act as a bidentate ligand, bond-
ing with metal cation through two sulfur atoms to form a
four-membered ring structure. Therefore xanthates are
commonly powerful collectors. But they suer from poor
selectivity and render the otation separation of copper/
iron sulde minerals need high lime consumption and the
operating pH values have to be above 13.
The HOMO eigenvalue of Z-200 was very low and the
electron-donating power of Z-200 was weaker than that
of butyl xanthate ion. The LUMO of Z-200 was constituted
by pz-orbits of every atom in AOAC(@S)ANA group and
could form back donation covalent bond by overlapping
of the d-orbits of metal cation on the mineral surface. While
the four-membered chelate ring formed between Z-200 and
metal cation would be unstable. The pKa of Z-200 was
above 12 (Basilio, 1989; Nagaraj et al., 1988; Fairthorne
et al., 1996) and Z-200 existed in molecule form during
the copper/iron otation separation commonly performed
at the pulp pH value about 11. Hence the collecting power
of dialkyl thionocarbamates for copper and iron sulde
minerals was decreased and its selectivity against iron sul-
de minerals was increased. In practice, the iron sulde
minerals were eectively rejected and the otation separa-
tion of copper/iron sulde minerals were performed at the
pulp pH value about 11 by using dialkyl thionocarbamates
as a collector. But dialkyl thionocarbamates were less pow-
erful than xanthate, which decreased the recoveries of cop-
per sulde minerals (Fairthorne et al., 1996).
IOECTCs HOMO eigenvalue was lowest and its elec-
tron-donating power was also weakest in three collectors
butyl xanthate ion, Z-200 and IOECTC, which meant
IOECTCs selectivity against iron sulde minerals was
the best. The LUMO of IOECTC was constituted by pz-
orbits of every atom in the AOAC(@O)ANAC(@S)AOA
group, which was a conjugated p-bond that would readily
accept and delocalize electrons. The copper having
(t2g)6(eg)3Cu(k) or t6e4Cu(j) conguration on the surface
of copper sulde minerals had richly d-orbital electrons
(feedback electrons). As a result, it was suggested that dur-
ing the interaction between ECTC collectors and copper
cation on the surfaces of copper sulde minerals, ECTC
1383
LUMO
Eigenvalues/a.u. Molecular orbital compositions
0.04204 px- and pz-orbits of every
atom in AOAC(@S)S group
0.00509 pz-orbits of every atom
in AOAC(@S)ANA group
0.03455 pz-orbits of every atom
in AOAC(@O)ANAC(@S)ANA group
oers its HOMO electrons of thiol sulfur atom to copper
cation, forming r-bond, and simultaneously, copper cation
donates its d-orbital electrons to the LUMO of ECTC,
forming dative p-bond. ECTC collectors will interact
chemically with copper on the surface of copper sulde
minerals to form a more stably six-membered complex
than butyl xanthate ion (Basilio, 1989; Yoon and Basilio,
1993; Mielczarski and Yoon, 1991; Shen et al., 1998).
Hence compared with xanthates and dialkyl thionocarba-
mates, ECTC collectors are more powerful for copper sul-
de minerals and more selective against iron sulde
minerals in alkaline and neutral pH conditions. ECTC col-
lectors should perform the otation separation of copper/
iron sulde minerals at a lower pH value than dialkyl
thionocarbamates.
4. Conclusions
The electron-donating power of xanthates is strong,
therefore it can strongly react with metal cation on the sur-
faces of copper and iron sulde minerals through forming
normal covalent bonds. This explains the poor selectivity
of xanthates and also the high pH values (above 13) required
for the otation separation of copper/iron sulde minerals.
Dialkyl thionocarbamates are more selective for copper sul-
de otation, particularly against gangue iron suldes.
Although less powerful than xanthates, dialkyl thionocar-
bamates can perform copper/iron otation separation at
lower operating pH (commonly at pH values below 11.5).
Ethoxycarbonyl thionocarbamates use an ethoxycarbonyl
replacing an alkyl N-substituent in dialky thionocarba-
mates. The presence of the ethoxycarbonyl group eectively
changes the functional group of collector from
AC(@S)NHA to AC(@S)NHC(@O)A. The strong elec-
tron-withdrawing ethoxycarbonyl group adjacent to C@S
group decreases the electron density of the sulfur, which
improves ECTCs selectivity against iron sulde minerals
at slightly alkaline conditions. ECTCs LUMO is consti-
tuted by pz-orbits of every atom in the conjugate
AOAC(@O)ANAC(@S)AOA group and pleased with
accepting richly d-orbital electrons (feedback electrons)
from (t2g)6(eg)3Cu(k) or t6e4Cu(j) conguration of copper
cation on the surface of copper sulde minerals. Hence the
interaction of ECTC with copper cation involves in forming
six-membered chelate ring, and the collecting power of
1384 G.-y. Liu et al. / Minerals Engineering 19 (2006) 13801384
ECTC for copper sulde minerals and their selectivity
against iron sulde minerals are improved at the same time.
References
Basilio, C.I., 1989. Fundamental studies of thionocarbamate interactions
with sulde minerals. Ph.D. Thesis, Virginia polytechnic institute and
state university, Blacksburg, Virginia.
Boulton, A., Fornasiero, D., Ralston, J., 2000. Depression of iron sulde
otation in zinc roughers. Minerals Engineering 14 (9), 10671079.
Fairthorne, G., Fornasiero, D., Ralston, J., 1996. Solution properties of
thionocarbamate collectors. International Journal of Mineral Process-
ing 46 (12), 137153.
Fairthorne, G., Fornasiero, D., Ralston, J., 1997. Interaction of thionoc-
arbamate and thiourea collectors with sulde minerals: a otation and
adsorption study. International Journal of Mineral Processing 50 (4),
227242.
Frisch, M.J., Trucks, G.W., Schlegel, H.B., et al., 1998. Gaussian 98,
Revision A.9. Gaussian, Inc., Pittsburgh PA, USA.
Fu, Y.-L., Wang, S.S., 1989. Neutral hydrocarboxycarbonyl thionocar-
bamate sulde collectors. American Cyanamid Company, US Patent
RE32827.
Fu, Y.-L., Wang, S.S., Nagaraj, D.R., 1986. Collectors and froth otation
processes for metal sulde ores. American Cyanamid Company, GB
Patent 2163068A.
Klopman, G., 1968. Chemical reactivity and paths. Journal of American
Chemical Society 90, 223230.
Liu, G.-y., 2004. Research on the comprehensive utilization for copper
sulde ores with new collectors. Ph.D. Thesis, Central South Univer-
sity, Changsha, Hunan.
Mielczarski, J.A., Yoon, R.H., 1991. Spectroscopic studies of the structure
of the adsorption layer of thionocarbamate 2 on the cuprous sulde.
Langmuir 7 (1), 101108.
Nagaraj, D.R., Brinen, J.S., 1996. SIMS and XPS study of the adsorption
of sulde collectors on pyroxene: A case for inadvert metal in
activation. Colloids and Surfaces A: Physicochemical and Engineering
Aspects 116 (3), 241249.
Nagaraj, D.R., Brinen, J.S., 2001. SIMS study of adsorption of collectors
on pyrite. International Journal of Mineral Processing 63, 4557.
Nagaraj, D.R., Wang, S.S., Frattaroli, D.R., 1986. Flotation of copper
sulde minerals and pyrite with new and existing sulfur-containing
collectors. In: Fielding, L.E., Gordon, A.R. (Eds.), Proc. 13th CMMI
Congress Metall., Singapore CMMI and Ausr. Inst. Min. Met., pp.
4957.
Nagaraj, D.R., Lewellyn, M.E., Wang, S.S., Mingione, P.A., Scanlon,
M.J., 1988. New sulde and precious metals collector: For acid,
neutral and mildly alkaline circuits. In: Forssberg, E. (Ed.), Proc.
XVIth International Mineral Processing Congress. Elsevier, Stock-
holm, Amsterdam, pp. 12211232.
Seryakova, I.V., Vorobiova, G.A., Glembotskii, A.V., 1975. Extraction of
metals by neutral sulfur-containing extractants. Part I. O-isopropyl-N-
ethylthionocarbamate. Anal Chim Acta 77, 183190.
Shen, W.Z., Fornasiero, D., Ralston, J., 1998. Eect of collectors,
conditioning pH and gases in the separation of sphalerite from pyrite.
Minerals Engineering 11 (2), 145158.
Wang, D., Lin, Q., Jiang, Y., 1996. Molecular design of reagents for
mineral and metallurgical processing, rst ed. Central South Univer-
sity of Technology, Changsha, pp. 88110.
Woods, R., Hope, G.A., 1999. A SERS spectroelectrochemical investiga-
tion of the interaction of O-isopropyl-N-ethylthionocarbamate with
copper surfaces. Colloids and Surfaces A: Physicochemical and
Engineering Aspects 146 (13), 6374.
Yoon, R.H., Basilio, C.I., 1993. Adsorption of thiol collectors on sulde
minerals and precious metalsa new perspectiveProc. XVIIIth Inter-
national Mineral Processing Congress, Congress, vol. 3. The Austral-
asian Institute of Mining and Metallurgy, Sydney, Melbourne, pp.
611617.