A STUDY OF ACID-GANGUE REACTIONS IN HEAP-LEACH

OPERATIONS

Ali Seyedbagheri, Petrus Van Staden & Chris Mclaren

Mintek Company, Randburg, South Africa

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

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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 Gangue Minerals

Silicate gangue minerals comprise more than 95 percent of most porphyry copper ores, with a few
important examples being listed in Table 1. Consequently, it can be expected that the behaviour of
these minerals in sulfuric acid solutions would exert an important influence on the performance of
copper and other heap leaching process [4]. They form a group of inorganic compounds of great
chemical, as well as structural, complexity. They are essentially divided into primary and secondary
silicate minerals depending on whether they are the original minerals (e.g. quartz, feldspar, mica,
amphibole, and pyroxene) or are formed by the dissolution, alteration and byproduct precipitation
of primary silicates. The secondary silicates in turn are divided into two groups including clay
minerals (e.g. illite, vermiculite, montmorillonite and kaolinite) and residual oxides and hydroxides.
Of the nine common cations in silicate rocks, only four (Si4+, Ti4+, Al3+, and Fe3+) form stable
oxides or hydroxides or both [5].

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 Table 1: Important silicate minerals present in porphyry copper deposits [4]

Mineral Ideal chemical formula Silicate type

Quartz SiO2 tecto
orthoclase
KAlSi3O8 tecto
(K-feldspar)
NaAlSi3O8 (albite) - CaAl2Si2O8
Plagioclase tecto
(anorthite)
Biotite K(Mg,Fe)3[(Al,Fe)Si3O10)](F,OH)2 phyllo
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 Al4Si4O10(OH)8 phyllo
Hornblende
(Ca,Na)2-3(Mg,Fe,Al)5Si6(Al,Si)2O22(OH)2 Ino (double chain)
(amphibole)
Actinolite Ca(Mg,Fe)3(SiO3)4 Ino (double chain)

Factors Determining Silicate Minerals Reactivity In Acidic Media

Silicate Structure
One common component of all silicates is the tetrahedral SiO4-4 structural sub-unit. The manner in
which these units associate provides a basis for classification of the silicates into six distinct groups.
They range from meso-(or ortho)-silicates in which the silica tetrahedra are independently joined by
some metal cations, thereby rendering the mineral very susceptible to acid attack, to the
tectosilicates, in which all oxygen atoms are shared between silicon atoms making the mineral
resistant to acid leaching. The other intermediary groups show a proportional reactivity depending
on the proportion of oxygen atoms shared by silica tetrahedra. Hence, from knowledge about the
silicate group that a specific mineral belongs to, an indication can be obtained of the reactivity of
the mineral and its potential to react with acid. This rough classification is illustrated in Figure 1
which illustrates Bowens reaction series of the order in which minerals crystallise from a magma.
Olivine
Hypersthene basalt, diabase Ca plagioclase
Increasing
Augite Ca-Na plagioclase
Si or other
Hornblende Na-Ca plagioclase cations with
increasing high energy
rate of Biotite mica potassic alteration Na plagioclase oxygen bonds
breakdown K Feldspar
quartz sericite alteration
in acid solutions
Muscovite

Sericite

Quartz

Figure 1: Common rock-forming (gangue) minerals arranged by crystallisation

order and dissolution kinetics in acid sulfate leach solutions [4]

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Metal Cation-Oxygen Bond
The metal cation-oxygen bonds in silicates are generally weaker than the silicon-oxygen bonds, and
are thus more susceptible to acid attack. Within a given silicate structural group, the reactivity is
determined to a large extent by the strength of the metal-oxygen bond and therefore by the nature of
metal cation [6]. Table 2 lists the strengths of some typical metal-oxygen bonds in oxygen
containing glasses and crystals, as estimated by Huggins and Sun [7].

Table 2: Metal-oxygen bond energy for some metal cations [7]

Ion Metal-oxygen bond energy Ion Metal-oxygen bond energy

(KJ mol-1) (KJ mol-1)

4+ 2+
Si 13012-13146 Mg 3816
4+ 2+
Ti 12058 Mn 3745
Zr4+ 11033 Cu2+ 3598
2+
Ca 3510
Al3+ 7201-7858 Pb2+ 3469
3+ 2+
Cr 7092 Sr 3347
3+ 2+
Y 6552 Ba 3213

Be2+ 4774
2+
Zn 3937 Li+ 1469
2+
Ni 3887 Na+ 1347
2+ +
Fe 3845 K 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 )
Chain-silicates like ussingite (Na2AlSi3O5(OH) )

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 Phyllosilicates containing appreciable ferric iron in the sheets (nontronite
Na0.3Fe+32(Si,Al)4O10(OH)2n(H2O))
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).

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.

Acid Anion and Mineral Interaction

Complexing of the metal ion with an anion derived from an inorganic acid can enhance the
dissolution rate of metal silicates. For example, the observed order of reactivity of acids toward the
silicate mineral chrysocolla ((Cu,Al)2H2Si2O5nH2O) is as follows:

H2SO4>HCl>HNO3>HClO4

With sulfuric acid being found to yield a faster rate of dissolution of chrysocolla than the other
acids, which can be explained by the relative strength of the metal cation-acid anion complexes [6].
Factors such as crystallinity, the presence of inclusions and dissolved impurities, grain size and
dislocations are also known to influence the rates of chemical reactions of all minerals. According
to Grim, for example [11], fine-grained chlorite can be decomposed in warm HCl, whereas well
crystallised chlorite can remain unattacked by 10 M HCl for over 72 hours. Therefore, in the
mineralogical report of an ore, the crystallinity should also be described.

Modelling of Acid-Siliicate Reactions in Heap Leaching

Stages In Silicate Mineral Dissolution/Alteration Reactions

The reactions between acid and silicate minerals can be regarded as an accelerated weathering
process, which proceeds along a similar sequence of stages as is found during natural weathering, as
illustrated in Table 3. Firstly, the primary minerals dissolve (either partially or completely) and
secondary minerals can result as remaining undissolved residues or re-precipitated
oxides/hydroxides. Leaching of elements such as calcium, magnesium, sodium, potassium, and
soluble silica supports further transformation processes. Successive secondary minerals can form
and be leached again, following a sequence of gradual loss of silica during each leaching step and
finally leaving secondary products that contain no silica, i.e., the hydrous oxides, while the leached
silica re-precipitates as secondary quartz. These minerals tend to persist as the final products of long
and intense silicate mineral leaching [5, 12].
As a result, the rigorous modelling of the performance of a heap leach operation requires a
complete set of all the reactions, and their equilibrium constants, in which the silicate minerals

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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 Primary Mineral Secondary Minerals
Mineral
Ti Anatise
Discrete Olivine
Fe Geotite
Tetrahedra Augite, Amorphous
1 Hematite
Single Chains Hypersthene Hydrous Oxides
Double Chains Al Gibbsite
Hornblende
Si Boehmite
Amorphous Volcanic Glass Fe
2 linked (basic) Amorphous
Al Gibbsite
Tetrahedra Zeolites Hydrous Oxides
Si Allophane
H, Ca
Trioctahedral Illite Ca
3- Layer K
K H - SiO2
Structures with Biotite Kaolin
3 Clay Vermiculite Ca Montmorillonite
Hexagonal Muscovite
K H H, Ca + SiO2
Linkages
Dioctahedral Illite K
Amorphous Volcanic Glass Amorphous Al Gibbsite
4 linked (acid) Hydrous Oxides Si
Tetrahedra Feldspars

Linked Silicic Acid Chalcedonite Silicic Acid

5 Quartz
Tetrahedra
Secondary Quartz

Current Modelling Tools for Acid-Gangue Reactions During Heap Leaching

The reaction stoichiometry and equilibrium data referred to above can be used in a geochemical
model to perform the simultaneous equilibrium calculations for the time and special elements into
which a heap leach operation can be discretisised for its numerical simulation.
Numerical models have been used for assessing the potential for the transport of soluble
species in mine waste dumps, which can obviously also be applied to heap leaching. Various
studies have also been undertaken on the modelling of mass and energy transport specifically in
ore heaps [13, 14, 15, 16].
The existing numerical flow and reactive transport models can be divided into three broad
categories: (a) water flow models, (b) geochemical models, and (c) models that integrate flow and
geochemistry.

Water flow models can be further divided into:

those that assume unsaturated water flow, saturated water flow, and surface water flow and
those that integrate flow between two or more of these domains.

Static geochemical models are typically equilibrium-based and include acid-base, oxidation-
reduction, aqueous complexation, precipitation-dissolution, ion exchange, adsorption-desorption,
and gas transfer reactions. However the prediction of contaminant or solution species transport as it

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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

HYDROCOPPER 2009, Antofagasta, Chile 74

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.

SUMMARY AND CONCLUSIONS

Obtaining ore samples from a prospective ore body by diamond core drilling is an expensive
undertaking, and it is important that as much as possible information is derived from those samples,
and that such information be interpreted to the maximum extent possible. Only in that way can
investors be provided with the best information for further investment decisions.
Acid consumption is likely to be one of the major, if not the dominating, operating cost element
during the life of a heap leach project. The blinding of a heap of ore by precipitates can terminate its
useful life, and the presence of elevated levels of nuisance elements in the liquor feed to the
downstream metals recovery plant can present significant operational problems. All these factors
are related to the gangue mineralogy and chemistry of the ore.
Even during the earliest stages of a project, when only a limited amount of sample may be
available, some estimates regarding acid consumption, re-precipitation in the heap and pregnant liquor
composition can already be made from the mineralogical characterisation of the gangue minerals.
In this paper, examples are provided of how the reactivity of various gangue minerals are
related to their general classification, chemical composition, and structure. This information can be
coupled to mathematical models and databases of various possible levels of sophistication to
simulate a commercial heap leach operation, to provide a level of interpretation that currently does
not seem to be common practice, and which is often delayed until only much later in the project
when tall column leach or pilot plant experiments are undertaken.

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