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ABSTRACT
During exploration projects, it is important to be able to predict, as early as possible, the
behaviour of an ore with respect to metal extraction. In the case of heap leach projects, where
gangue is the major constituent of the feed material being treated, the anticipated gangue-acid
consumption (affecting operating cost) and the associated alteration and precipitation
reactions (affecting heap permeability) are equally important. A survey of the literature on the
mineralogy of porphyry-copper resources indicates that silicates with a high extent of
polymerisation of the silica tetrahedral structure have a relatively low tendency to react with
acid. Hence, most of these silicates tend to undergo merely alteration reactions in contact with
acid (as opposed to breaking down to their elements), and precipitate alteration products in the
process. Plagioclase feldspars tend to dissolve under acidic conditions in a heap and create
gelatinising silicate minerals as alteration products which can blind the ore particles and lead
to a heap with poor permeability. Biotite and chlorite are examples of slow acid consumers and
their dissolution is proportional to the acid strength. Quartz, alkali feldspars, and
phyllosilicates are slightly reactive gangue minerals and dissolve in acid very slowly. An
outline is provided of how information regarding the chemistry of silicate-gangue minerals can
be incorporated into a model to serve as a tool for the early prediction of larger scale heap
leach performance from laboratory scale investigations on small samples.
INTRODUCTION
Ores considered for heap leaching are sometimes evaluated without adequate attention to the
gangue mineralogy, despite the fact that ore and gangue mineralogy is probably the single most
important parameter affecting operational costs and recoveries and can change significantly from
one area of the resource to another. Apparently minor changes in gangue mineralogy can have a
significant impact on the requirements for curing and agglomeration, and on the acid consumption,
metal extraction, and PLS solution chemistry observed during leaching [1]. Adams [2] has
considered several examples of the impact of mineralogical composition on process performance,
and argues for the necessity of having an automated mineralogical analysis to serve as a useful
predictor of expected plant performance. Baum suggests that any results of chemical acid
consumption must be supported by mineralogical acid consumption data [1]. In order to maximise
the efficiency of metal recovery while minimising the consumption of acid by gangue, a wide range
of mineralogical aspects needs to be considered [3].
Certain gangue minerals, like calcite (CaCO3), are very reactive to acid and will in time dissolve
completely in contact with even very dilute sulfuric acid. Ores that contain a significant proportion
of such minerals will be clearly unsuitable for acidic heap leaching and as such represents a trivial
case for gangue chemistry studies.
However, large groups of the silicate gangue minerals found in igneous rock react incompletely
with sulfuric acid and with several of them the extent of acid-gangue reaction is a function of the
acid strength in the leach liquor. The moderate reactivity to acid of these gangue minerals limits
their acid consumption sufficiently, such that acid heap leaching of the ore can be economically
viable with relatively low valuable metal grade. It leaves a margin of control over the acid
consumption, and permits an economic optimum to be sought between acid cost and leach kinetics,
by varying the acid curing parameters and the acidity of the irrigation liquor.
This further implies that from an understanding of the reactions between particularly the silicate
gangue minerals and sulfuric acid, it is possible to make predictions about the likely acid
consumption of the ore under various conditions of irrigation acid strength, and from that can
follow predictions about the precipitates that are likely to form inside the heap, as well as the (both
valuable and nuisance) soluble species that are likely to report to the pregnant leach liquor feeding
the downstream recovery steps. Such predictions can already start to be made during the earliest
phase of a project, when only a limited amount of drill core sample may be available, based on a
knowledge of the gangue mineralogy, coupled to geochemical database information and modelling
software. Deriving this type of information should not be based only on very crude scale-up factors
from small-scale tests, and should not be delayed until large ore samples are made available for
column leach tests.
Silicate type
Quartz
orthoclase
(K-feldspar)
SiO2
tecto
KAlSi3O8
tecto
Biotite
Chlorite
(Mg,Fe)5Al(Si3Al)O10(OH)8
phyllo
muscovite/sericite
KAl2(Si3AlO10)(F,OH)2
phyllo
Montmorillonite
(Na,Ca)0..3 (Al,Mg)2Si4O10(OH)3.nH2O
phyllo
Vermiculite
(Mg,Fe,Al)3[(Al,Si)4O10](OH)2.4H2O
phyllo
Kaolinite
Hornblende
(amphibole)
Actinolite
Al4Si4O10(OH)8
phyllo
(Ca,Na)2-3(Mg,Fe,Al)5Si6(Al,Si)2O22(OH)2
Ca(Mg,Fe)3(SiO3)4
Plagioclase
tecto
phyllo
basalt, diabase
Augite
increasing
rate of
breakdown
in acid solutions
Hornblende
Biotite mica
Ca plagioclase
Ca-Na plagioclase
Na-Ca plagioclase
potassic alteration
Na plagioclase
Increasing
Si or other
cations with
high energy
oxygen bonds
K Feldspar
quartz sericite alteration
Muscovite
Sericite
Quartz
Ion
(KJ mol-1)
Si
4+
13012-13146
Mg
2+
3816
2+
3745
4+
12058
Mn
Zr4+
11033
Cu2+
3598
2+
3510
Pb2+
3469
2+
3347
2+
3213
Ti
Ca
Al3+
Cr
3+
7201-7858
7092
Sr
3+
6552
Be2+
4774
2+
3937
Li+
1469
Ni
2+
3887
Na+
1347
Fe
2+
Zn
3845
Ba
1251
The bond energies in Table 2 suggest that the resistance to acid attack of a silicate mineral will
increase with an increasing proportion of silicon and other high bond-energy metals. A practical
example illustrating this principle can be found in the comparison between biotite and muscovite
(Table 1), both being phyllosilicates of very similar composition except that muscovite has Al in
the structure instead of the Fe and Mg of biotite. Snall [Snall et al. 2000], in his silicate reactivity
studies, showed that biotite dissolved completely in acid, while muscovite dissolution was only
5.6 to 8.7 percent. As a result, it is found in heap leach operations that muscovite remains almost
unreacted in contact with acid, whereas biotite is an acid consumer and its extent of dissolution is
proportional to the strength of the acid that it is in contact with. The magnesium contained in
biotite tends to hydrolyse quite readily, while the ferrous iron oxidizes, resulting in biotite
alteration products.
Gelatinising silicates provide a good example of the influence of silicate structure and metal
oxygen bond factors on the chemical behaviour of minerals. Silicate mineral groups that gelatinise
under acid attack are:
Silicate minerals of small molecular weights, like nesosilicates (e.g. olivine (Mg,Fe)SiO4),
sorocilicates (e.g. kermanite Ca2MgSi2O7), and silicates containing ring structures of three
silicon atoms (e.g. catapleiite Na2ZrSi3O92H2O )
Tectosilicates containing aluminium in their structure in the ratio of at least two aluminium
atoms to three silicon atoms like nepheline {(K,Na)AlSiO4}, anorthite (CaAl2Si2O8) and natrolite
(Na2Al2Si3O10 2H2O).
ferric
iron
in
the
sheets
(nontronite
A complete list of gelatinising minerals is given by Terry and Murata [Terry part II, 1983, Murata
1943]. Gel formation in a heap can obviously interfere with the permeability of the ore, whereas
elevated levels of silica in the pregnant leach solution can interfere with the operation of the solvent
extraction and electrolysis stages. It is therefore important to be able to predict when significant
dissolution of silica is likely to occur so that precautions can be taken to reduce the likelihood of
silica dissolution and gelatinisation. Measures that can be taken in this regard include moderation of
the acid regime used for curing and leaching, and intermittent irrigation to promote cyclic
precipitation in the heap of the potential gel-forming species before polymerisation with the
concomitant water encapsulation occurs.
present in the ore under study, can participate, from their original form up to its complete
decomposition.
Table 3: Stages in dissolution/alteration and precipitation of silicate minerals [4]
Silicate Structure
Group of Primary
Mineral
Secondary Minerals
Primary Mineral
Discrete
Tetrahedra
Single Chains
Double Chains
Olivine
Augite,
Hypersthene
Hornblende
Amorphous
linked
Tetrahedra
(basic)
Amorphous
Hydrous Oxides
Volcanic Glass
Zeolites
Amorphous
Hydrous Oxides
Ti
Fe
Anatise
Geotite
Hematite
Gibbsite
Boehmite
Al
Si
Fe
Al
Si
Gibbsite
Allophane
H, Ca
3- Layer
Structures with Biotite
Hexagonal
Muscovite
Linkages
Amorphous
linked
Tetrahedra
Linked
Tetrahedra
Trioctahedral Illite
K
K
H
Ca
Clay Vermiculite
K
H
H, Ca
K
Dioctahedral Illite
Volcanic Glass
(acid)
Feldspars
Amorphous
Hydrous Oxides
Quartz
Silicic Acid
Al
Si
Ca
- SiO2
Montmorillonite
+ SiO2
Kaolin
Gibbsite
Chalcedonite
Silicic Acid
Secondary Quartz
those that assume unsaturated water flow, saturated water flow, and surface water flow and
Static geochemical models are typically equilibrium-based and include acid-base, oxidationreduction, aqueous complexation, precipitation-dissolution, ion exchange, adsorption-desorption,
and gas transfer reactions. However the prediction of contaminant or solution species transport as it
occurs in heap leaching requires integration of flow and geochemical processes. This integration
can range from a simple mixing cell approach to fully coupled multicomponent reactive transport
formulations with the possible inclusion of equations to account for slow reaction kinetics [17], that
is reactions that do not proceed to equilibrium.
A number of computer models are available for integrating water flow, oxygen transport, and a
broad range of geochemical reactions to predict the movement of contaminants in the subsurface
[18, 19, 20, 21]. These models have been applied to a number of mine sites representing a range of
climatic settings. For example, reactive solute transport models have been applied to assess solute
release from coal mines and to evaluate closure scenarios. In general, the quality of the predictions
is related to the quality and amount of data used for the calculations and the complexity of
processes included. Examples of existing models mentioned in the literature are listed below, some
of which are in the public domain, and some are proprietary codes, while others were developed for
research applications only.
Model Categories
Saturated Water Flow through Porous Media (not suitable for fractured media): e.g. MODFLOW
Unsaturated Water Flow through Porous Media
e.g. SEEPW, HYDRAS, HYDRAS2D
Saturated Water Flow through Fractured Media:
e.g. FRAC3DVS, FRACTRAN, NETFLO, SWIFT-98, TRAFRAP-WT
Unsaturated Water Flow through Fractured Media:
e.g. FRAC3DVS
Surface Water Flow:
e.g. HEC-RAS
Geochemical Equilibrium Models:
e.g. MINTEQA2, PHREEQC, GEOCHEMISTS WORKBENCH, MODPHRQ
Reactive transport models (Integrated flow and Geochemical models):
e.g. PHREEQC, MINTRAN, FLOTRANS, HYDROGEOCHEM, UNSATCHEM,
Reactive Solute Transport Models Incorporating Sulfide Oxidation Reactions:
MINTOX, MIN3P, MULTIFLOW, POLYMIN
Sulfide Oxidation Models:
e.g. PYROX, SULFIDOX
For early-stage investigations, it is probable that insufficient input information will be available to
warrant the use of a sophisticated proprietary model, but already valuable insights can be gained
from simply a mineralogical study of the gangue and holistic stoichiometric calculations over the
life time of a heap. Sophistication can be added to these calculations by discretisising the process
spatially and in time, with the outputs from earlier elements providing the inputs for later elements.
For the simultaneous solution of the stoichiometry while satisfying all equilibrium constants,
acquiring one of the existing models (many of which include extensive databases) would in most
cases be warranted, as opposed to attempting to develop the required software and developing the
entire database in-house.
The shortfalls of even the best and latest solution chemistry theory and models are commonly
known. But despite that, the undertaking of at least some level of theoretical calculation of the
gangue stoichiometry to be expected from an ore over the life time of a heap, based on its
mineralogical information, is a level of interpretation that is worth undertaking at the earliest stage
of a project, but which currently does not seem to be common practice.
REFERENCES
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troubleshooting in copper leach operations. Proceedings of Copper 99 Cobre 99
International Conference, Volume IV, Hydrometallurgy of copper, p.p. 393-407. [1]
Adams, M. D. (2007). Towards a virtual metallurgical plant 2: Application of mineralogical data.
Minerals Engineering, 20, p.p. 472-479. [2]
Jansen, M. & Taylor, A. (2003). Overview of Gangue Mineralogy Issues in Oxide Copper Heap
Leaching. ALTA 2003 copper - 8: technical proceedings - Global technical interchange,
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