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Abstract
Copper retention due to chemical and physical interaction with reactive gangue has been studied during sulphuric acid
leaching of atacamite, chrysocolla and malachite, using a synthetic rock (57% quartz, 42% reactive gangue and 1% ore).
Smectite- and mordenite-rich gangues represent the highest copper retention whereas the lowest is found for kaolinites and illite.
During leaching, smectites show the largest change (increase) in volume; no volume change occurred for kaolinites, zeolite and
illite. Kaolinite-rich gangue forms barriers due to de-lamination demonstrated by acid accumulation at the top of the columns.
The X-ray diffraction patterns of smectite, illite and kaolinite in the residues demonstrate the diminution or complete loss of
basal crystal faces accompanied by the neo-formation of alunogen, meta-alunogen, coquimbite and goldichite. These new
phases contribute to a temporary reduction of permeability. For all the synthetic rocks assayed, the copper retention is directly
proportional to cation exchange capacity (CEC) of the starting materials, and corroborated by the CEC of Cu of the residues
determined without water elution prior to analysis.
This test used represents a predictive tool to evaluate the potential Cu retention and gangues with elevated CEC.
D 2005 Elsevier B.V. All rights reserved.
Keywords: Acid leaching; Copper ores; Reactive gangue
1. Introduction
Oxidised copper ores, consisting mainly of silicates
(chrysocolla, a mineraloid with cited formula (Cu,Al)2
181
non-traditional chemical and mineralogical characterization in a short and severe acid leaching test. These
ore minerals, atacamite, chrysocolla and malachite,
were selected for their importance for Chilean copper
deposits and availability of pure materials.
The criteria for selection of the gangue were the
reactivity due to charge deficiencies per formula unit,
expandability, the cation adsorption and exchange
capacities (CEC), the possibility of physical barrier
formation, relevance for Chilean exotic copper-ore
deposits, and on an experimental level, purity, homogeneity and availability of the materials.
2. Methods
2.1. Experimental setup
The short-term leach tests were carried out with a
strong solution of sulphuric acid (265 g/L) at ambient
temperature (18 to 21 8C) in small columns (Fig. 1)
using a synthetic rock composed of 57% quartz, 1%
ore phase, and 42% reactive gangue. Synthetic rock
compositions used in this study represent extreme
scenarios to demonstrate the interaction of ore and
phyllosilicate or zeolite gangue without the need for
concentrations steps, as would be required for the
routine X-ray diffraction (XRD) control for phyllosilicates. A blank series of 58% quartz and 42% reactive gangue acted as non-mineralized control for each
gangue type. A pure quartz sample (99% quartz and
1% ore mineral) was used to monitor complete ore
dissolution during leaching and the contribution of Si
from quartz to the leachate.
The mixtures were compressed to the consistency
of a semi-consolidated sediment at 40 ton/cm2.
Quartz was added as binertQ as permeabilizer to
avoid the formation of instant hydraulic barriers for
smectite type gangues. Details of the preparation of
artificial mineralized rock and leaching setup have
been published elsewhere (Kelm and Helle, 2003).
The high sulphuric acid concentration of 265 g/L
permits one to obtain information about the removal
of ions from the gangue silicates within a very short
period of time compared to bottle leachings using
mine acid concentrations. Ore minerals were obtained
from Chuquicamata Mine, CODELCO NORTE
(chrysocolla), Aldrich chemicals (malachite) and
182
SAZ
SWY
KGA-2
KGA-1
BL
Fig. 1. Experimental laboratory columns. Smectites (SAZ and SWY) kaolinites (KGA-1 and KGA-2) and BL (blank). Line on glass marks
original filling level of columns. Note the volume increase for SAZ and SWY smectite.
Table 1
Reactive gangue, mineralogy (XRD), cation exchange capacity (CEC) and specific surface area (BET) of the b200 Tyler mesh fraction
Reactive gangue
Mineralogy by XRD
CEC
(cmol/kg)
BET
(m2/g)
132
118
90
71
62
18
12
0.6
126
147
117
97
180
97
141
180
183
counts/second
9000
0
3
15
21
27
2 theta
Fig. 2. XRD patterns of heads (dark line) and residues (pale line) of smectites BENT-R, NAU, SWY and SAZ. Quartz (Q), coquimbite (coq),
alunogen (alun) and smectites (arrows). Broad arrow marks basal (001) smectite reflections.
184
%Cu(t) A Head
%Cu(t) C Residue
%Cu(t) C Head
%Cu(t) M Residue
%Cu(t) M Head
0,600
0,500
% total Cu
0,400
0,300
0,200
0,100
Quartz
MORD
IMT Illite
KGA-2 Kaolinite
KGA-1 Kaolinite
NAU Nontronite
BENT Rock
SWY Smectite
SAZ Smectite
0,000
Fig. 3. Total copper in the head and residues of malachite (M), atacamite (A) and chysocolla (C) series.
Malachite Series
45
40
30
25
20
15
10
5
Fig. 4. Copper retention (%) in the residues of malachite, atacamite and chysocolla series.
Quartz
MORD
IMT Illite
KGA-2 Kaolinite
KGA-1 Kaolinite
NAU Nontronite
BENT Rock
SWY Smectite
0
SAZ Smectite
Cu retention (%)
35
M-Series
A Series
C Series
185
CEC Head
120
cmol/kg
100
80
60
40
20
Quartz R
MORD R
IMT Illite R
KGA-2
Kaolinite R
KGA-1
Kaolinite R
NAU
Nontronite R
BENT Rock R
SWY
Smectite R
SAZ Smectite
R
Fig. 5. Total CEC of the residues of blank (BL), malachite (M), atacamite (A) and chysocolla (C) series. CEC head calculated from CEC of
starting materials.
in the remaining cation exchange positions, (2) retention of Cu as suspended gel or in water within the
residues. This second option could be favored if abundant cations are made available by the silicate gangue,
as happened in three of the smectite species. The more
acid stable SWY montmorillonite retains comparatively less copper, but at the same time maintains its crystal
structure, suggesting as for the acid resistant mordenite,
Cu retention in charge compensation positions.
These phenomena repeat for all three ores studied,
irrespective of the total Cu of 0.5% for atacamite and
malachite and 0.25% for chrysocolla (Fig. 3).
There is a good correlation between the total exchange capacity of the residues (considering remnant
cation proportion) (Fig. 5) and the total CEC of the
starting materials (Table 1). Finally, comparing Figs. 4
and 5 it is possible to say that the CEC is directly related
to copper retention of the ores and reactive gangues
studied.
Therefore this study shows that the parameter of
cation exchange capacity, when applied as a straightforward interchange procedure without water elution of
the residue to wash out remaining solution or gels, does
not permit one to pinpoint the location of the retained
copper; however, it reflects well the overall capability
of a gangue to retain copper in the residue, the principal
concern in mineral processing. A single step exchange
is easy to implement in many mining laboratories on
site. Applications of CEC to natural mineralized ore
can be a very efficient predictive tool for potential
copper retention.
4. Conclusions
The highest copper retention is found for smectites
and mordenite gangue; the lowest is observed for kaolinite, illite and quartz. The use of CEC without prior
elution of the residue with water provides a measure for
the overall Cu retention which may either be due to
cation exchange capacity, surface adsorption or, in the
case of an expandable phase, retention of solution or gel
in the residue. Together with the XRD analysis focused
on the possible presence of clay mineral phases, the
CEC represents a powerful predictive tool for Cu retention by clay mineral and zeolite phases. Both methods are easy to implement on a production site. As a
complement to traditional mineralogical characterization, the combination of CEC and XRD analyses incorporates a robust knowledge of ganguesolution
interaction during leaching and the potential loss of
copper and its retention in minerals with elevated CEC.
Acknowledgements
This research was made possible by the FONDECYT Grant 1010823 bThe interaction of oxide zone
copper minerals and gangue during leaching: a geometallurgical and experimental perspectiveQ. Staff at
the GEA Institute is thanked for their help with the
analytical work. The helpful comments and suggestions of two anonymous reviewers are very much
appreciated.
186
References
Bartlett, R.W., 1992. Solution mining. Leaching and Fluid Recovery
of Materials. Gordon and Breach Science Publishers, Philadelphia, USA.
Bideaux, A., Nichols, B., 1995. Handbook of Mineralogy, Part 1.
Mineral Data Publishing, Tucson, AZ. 446 pp.
Chipera, S.J., Bish, L., 2001. Baseline studies of the clay minerals
society clays: powder X-ray diffraction analyses. Clays and
Clay Minerals 49 (5), 398.
Clay Mineral Society (CMS) of America, 2004. http://www.clays.
org/sourceclays/SourceClaysData.html.
Dinelli, E., Tateo, F., 2002. Different types of fine-grained sediments associated with acid mine drainage in the Libiola FeCu
mine area (Ligurian Apennines, Italy). Applied Geochemistry
17, 1081.
Doula, M., Ioannou, A., Dimirkou, A., 2002. Copper adsorption and
Si, Al, Ca, Mg and Na release from clinoptilolite. Journal of
Colloid and Interface Science 245, 237.
Elzeo, J., Murray, H.H., 1994. Bentonite. In: Carr, D.D. (Ed.),
Industrial Minerals and Rocks, 6th edition. Society for Mining,
Metallurgy, and Exploration Inc., Littleton, CO, p. 233.
Fonseca, C., Cardoso, C., Martins, E., Vairinho, M., 1992. Selective
chemical extraction of Cu from selected mineral and soil sam-