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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
*
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
Feed Feed
Copper conc. Sulfur conc. Tailings Copper conc. Sulfur conc. Tailings
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 1383
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 LUMO
of sulfur
Eigenvalues/a.u. Molecular orbital Eigenvalues/a.u. Molecular orbital compositions
compositions
Butyl xanthate 0.3466, 0.03129 pz-orbit of S atoms 0.04204 px- and pz-orbits of every
ion 0.2952 in C(@S)S group atom in AOAC(@S)S group
Z-200 0.3203 0.20686 px-orbit of S atom 0.00509 pz-orbits of every atom
in C@S group in AOAC(@S)ANA group
IOECTC 0.1811 0.21642 px- and py-orbits of S 0.03455 pz-orbits of every atom
atom in C@S group in AOAC(@O)ANAC(@S)ANA group
to metal cation on the mineral surfaces to form normal oers its HOMO electrons of thiol sulfur atom to copper
covalent bond. At the same time, the LUMO of butyl xan- cation, forming r-bond, and simultaneously, copper cation
thate ion could overlap the d-orbits of metal cation on the donates its d-orbital electrons to the LUMO of ECTC,
mineral surface to form back donation covalent bond. forming dative p-bond. ECTC collectors will interact
Butyl xanthate ion would act as a bidentate ligand, bond- chemically with copper on the surface of copper sulde
ing with metal cation through two sulfur atoms to form a minerals to form a more stably six-membered complex
four-membered ring structure. Therefore xanthates are than butyl xanthate ion (Basilio, 1989; Yoon and Basilio,
commonly powerful collectors. But they suer from poor 1993; Mielczarski and Yoon, 1991; Shen et al., 1998).
selectivity and render the otation separation of copper/ Hence compared with xanthates and dialkyl thionocarba-
iron sulde minerals need high lime consumption and the mates, ECTC collectors are more powerful for copper sul-
operating pH values have to be above 13. de minerals and more selective against iron sulde
The HOMO eigenvalue of Z-200 was very low and the minerals in alkaline and neutral pH conditions. ECTC col-
electron-donating power of Z-200 was weaker than that lectors should perform the otation separation of copper/
of butyl xanthate ion. The LUMO of Z-200 was constituted iron sulde minerals at a lower pH value than dialkyl
by pz-orbits of every atom in AOAC(@S)ANA group and thionocarbamates.
could form back donation covalent bond by overlapping
of the d-orbits of metal cation on the mineral surface. While 4. Conclusions
the four-membered chelate ring formed between Z-200 and
metal cation would be unstable. The pKa of Z-200 was The electron-donating power of xanthates is strong,
above 12 (Basilio, 1989; Nagaraj et al., 1988; Fairthorne therefore it can strongly react with metal cation on the sur-
et al., 1996) and Z-200 existed in molecule form during faces of copper and iron sulde minerals through forming
the copper/iron otation separation commonly performed normal covalent bonds. This explains the poor selectivity
at the pulp pH value about 11. Hence the collecting power of xanthates and also the high pH values (above 13) required
of dialkyl thionocarbamates for copper and iron sulde for the otation separation of copper/iron sulde minerals.
minerals was decreased and its selectivity against iron sul- Dialkyl thionocarbamates are more selective for copper sul-
de minerals was increased. In practice, the iron sulde de otation, particularly against gangue iron suldes.
minerals were eectively rejected and the otation separa- Although less powerful than xanthates, dialkyl thionocar-
tion of copper/iron sulde minerals were performed at the bamates can perform copper/iron otation separation at
pulp pH value about 11 by using dialkyl thionocarbamates lower operating pH (commonly at pH values below 11.5).
as a collector. But dialkyl thionocarbamates were less pow- Ethoxycarbonyl thionocarbamates use an ethoxycarbonyl
erful than xanthate, which decreased the recoveries of cop- replacing an alkyl N-substituent in dialky thionocarba-
per sulde minerals (Fairthorne et al., 1996). mates. The presence of the ethoxycarbonyl group eectively
IOECTCs HOMO eigenvalue was lowest and its elec- changes the functional group of collector from
tron-donating power was also weakest in three collectors AC(@S)NHA to AC(@S)NHC(@O)A. The strong elec-
butyl xanthate ion, Z-200 and IOECTC, which meant tron-withdrawing ethoxycarbonyl group adjacent to C@S
IOECTCs selectivity against iron sulde minerals was group decreases the electron density of the sulfur, which
the best. The LUMO of IOECTC was constituted by pz- improves ECTCs selectivity against iron sulde minerals
orbits of every atom in the AOAC(@O)ANAC(@S)AOA at slightly alkaline conditions. ECTCs LUMO is consti-
group, which was a conjugated p-bond that would readily tuted by pz-orbits of every atom in the conjugate
accept and delocalize electrons. The copper having AOAC(@O)ANAC(@S)AOA group and pleased with
(t2g)6(eg)3Cu(k) or t6e4Cu(j) conguration on the surface accepting richly d-orbital electrons (feedback electrons)
of copper sulde minerals had richly d-orbital electrons from (t2g)6(eg)3Cu(k) or t6e4Cu(j) conguration of copper
(feedback electrons). As a result, it was suggested that dur- cation on the surface of copper sulde minerals. Hence the
ing the interaction between ECTC collectors and copper interaction of ECTC with copper cation involves in forming
cation on the surfaces of copper sulde minerals, ECTC 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 Nagaraj, D.R., Brinen, J.S., 1996. SIMS and XPS study of the adsorption
against iron sulde minerals are improved at the same time. of sulde collectors on pyroxene: A case for inadvert metal in
activation. Colloids and Surfaces A: Physicochemical and Engineering
Aspects 116 (3), 241249.
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