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Cyanidation of Refractory Gold Ores: A Review

Conference Paper July 2014

DOI: 10.13140/2.1.4772.6407

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 204

Cyanidation of Refractory Gold Ores: A Review

R.K. Asamoah, R. K. Amankwah and J. Addai-Mensah
Ian Wark Research Institute, The ARC Special Research Centre for Particle and Material Interfaces, University of
South Australia, Mawson Lakes, Adelaide, SA 5095, Australia

Mineral Engineering Department, University of Mines and Technology, Tarkwa, Ghana

Asamoah, R. K., Amankwah, R. K. and Addai-Mensah, J. (2014), Cyanidation of Refractory Gold Ores: A
Review, 3rd UMaT Biennial International Mining and Mineral Conference, pp204-

Abstract
The insusceptibility of gold ores to conventional cyanidation is defined by its mineralogical information and exacerbated by the
continuous decline in gold grade. The depletion of readily amenable gold ores and discovery of complex deposits inspire
knowledge improvement and search of commercially effective technique in extracting gold from refractory gold ores. This paper
reviews the causes, challenges, concerns and approach towards refractory gold ore cyanidation, considering the conceptual and
historical perspectives. It considers the diverse processing approach (route)neededto render refractory gold ores amenable to
cyanidation. Directions for future research in processing refractory gold ores has been stated.

1 Introduction Table 1 Classification of Refractory Gold Ores

Based of Degree of Refractoriness. Modified after
Cyanide remains the universal ligand for gold Amankwah et al. (2013)
extraction. It exhibitsseveral advantages (low cost,
great effectiveness for gold dissolution, and Classification Gold recovery
selectivity for gold over other metals) overother Free milling More than 95%
ligands (halides, thiosulphate, thiourea, and Mildly refractory 80 - 95%
thiocyanate) capable ofextracting gold. The use of
Moderately refractory 50 - 80%
cyanide in leaching system is
termedcyanidation(Habashi, 1970; Marsden and Highly refractory Less than 50%
House, 2006). Despite the success of cyanidation, its
applicability is limited by some gold mineralization.
These types ofgoldmineralisation are referred to as 2 Causes of Ore Refractoriness
refractory gold ores(Turney et al., 1989). Depletion
Gold ore refractoriness vary withgoldmineralisation.
of amenable ores alert researchers to decipher the
polylemma associated with treating refractory ores. These mineral associations occur during concomitant
The degree of refractoriness has been classified based geological leaching, concentration and deposition of
on the proportion of gold recovered (Table 1). gold minerals in the earth crust(McKibben,
Cyanidation can only be useful if by it, gold present 2005).Causes of refractory gold ores can also be
is economically recovered with high efficiency.This classified based on gangue mineral association
into(Turney et al., 1989; Afenya, 1991):
paperreviews the causes, challenges, concerns and
approach towards refractory gold ore cyanidation, Physically locked gold;
considering the conceptual and historical Chemically locked gold;
perspectives. The review will show evidence of
Reactive gangue minerals;
variation in ore characteristics with continuous gold
Adsorption of gold; and
processing, depth and possible ore characteristics in
the near future. It will also discuss previous and Passivation of gold.
recent discoveries on cyanidation of complex ores to Some complex gold ore deposits exhibit a
help predict the direction of future research in gold combination of the above effects making them more
extraction. complex for gold extraction.

204
 205
2.1 Physically Locked Gold
Gold in this classification exist in the free state,
occluded and/or disseminated, within the cyanide-
insoluble gangue minerals (silicates, sulphides and
oxides)(Fig. 1)(Bache, 1987; Spry and Thieben,
2000).
2.1.1 Formation of Physically Locked Gold
Gold can be physically locked by silicates, oxides
and sulphides. Its formation is primarily by natural
dissolution, concentration and precipitation
processes. Evidence of these natural processes have
been studied extensively (Boyle, 1979; Mann, 1984;
Michel, 1987;Colin et al., 1989; Vlassopoulos and
Wood, 1990;Benedetti and Boulgue, 1991; Greffi
et al., 1996; Bowell et al., 1999; Mohammadnejad et
al., 2013). Mohammadnejad et al. (2013)proposed
that dissolved gold is reduced and deposited on the
surface of silicate minerals.Sulphides are also known
to reduce dissolved gold (Marsden and House, 2006).
Hydrothermal activities after deposition lead to
physical locking of gold. Bowell et al.
(1999)associated gold silica intergrowth to
colloidal transport of Au in hydrothermal solutions.
Earlier research by Saunders (1990) showed that
coagulation of colloidal silica leads to trapping of
gold colloids. Frondel (1938)intensively studied the
stability of colloidal silica. Gold in these minerals
mostly occur as submicroscopic to sizable
grains(Bowell et al., 1999; Coetzee et al., 2011).
Various research have been done on this type of
refractory ore (Deep West Orebody, Jokisivu Ore,
Getchell Ore, etc)(Bowell et al., 1999; Hausen, 2000;
Liipo, 2003). Research by Liipo (2003) showed that
50% of gold in Jokisivu pilot feed and products was
locked up mainly in silicates which reported at
tailings after cyanidation. Gold in the Carlin-type
deposit was reported to be ultramicrometer native
gold inclusions, not as isomorphous substitution
(Mao, 1991).
Fig. 1 Schematic diagram of physically locked
gold in pyrite, quartz and/or iron oxide. Modified
after Ellis (2003)
205
In lateritic system, gold is associated in various forms
of oxides(Enzweiler and Joekes, 1991; Greffi et al.,
1996). The contact made by gold with oxide
especially, iron oxide has been explained by the
oxidation reduction reactions between Fe2+/Fe3+ and
Au3+/Au0 forming metallic gold. This model explains
the intergrowth of gold and iron oxide (Mann,
1984;Greffi et al., 1996).Greffi et al.
(1996)Concluded that, in natural system, where redox
processes may take place, gold will be transported as
colloidal Auo adsorbed or trapped in iron oxides.
2.2 Chemically Locked Gold
Gold in this type is concentrated chemically by its
host. Typically, gold is lattice-bound in sulphides and
gold-bearing tellurides(Cook and Chryssoulis, 1990;
Cook et al., 2009). Spectrographic techniques have
proved that gold, in some deposits(Sandaowanzi
deposit, Tissa-Sarkhoi province, Golden Sunlight
deposit, Kassiteres-Sappes area, Emperor gold
deposit, etc.), is chemically combined within
sulphideand telluride minerals rather than as discrete
metals inclusions (Cook and Chryssoulis, 1990; Spry
et al., 1997; Mao, 1991; Spry and Thieben, 2000;
Pals et al., 2003; Voudouris et al., 2006; Zoheir and
Akawy, 2010;Gonzlez-anaya et al., 2011; Adams,
2013; Liu et al., 2013).The worlds biggest newly
discovered gold-telluride deposit (Early Cretaceous
Sandaowanzi deposit, northeast China),
contains>95% gold. The highest gold grade
registered was 20,000 g/t (Liu et al., 2011; Liu et al.,
2013).
2.2.1 Formation of Chemically Locked Gold
Electronic and structural investigation by Chen et al.
(2014) revealed that, gold would most likely exist in
pyrite by incorporating into interstitial lattice sites
and by substituting for S atoms (Fig. 2). Their
calculations showed that, gold was present as Au1+ in
pyrite. The co-occurrence of tellurium with noble
metals such as gold and silver was attributed to the
semi-metallic nature of tellurium (Zhang et al.,
2010). Major investigations showed that, this
mineralisation occur as a result of hydrothermal
alteration of granites, diorites, and effusive rocks at
temperature in the range 70 280 C. As temperature
decreases, the activity of tellurium in hydrothermal
fluid increases, therefore its formation in epithermal
deposits.Most telluride associations are in porphyry
gold deposits where the occurrence of gold
mineralization is in volcanoplutonic belt. Gold-
telluride formation and phase relations (among
 206
tellurides, sulphides and oxides) have been studied
extensively (Afifi et al., 1988; Bortnikov et al., 1988;
Damdinov et al., 2007;Taylor, 2009;Liu et al., 2011;
Liu et al., 2013). Fig. 3 shows the four type possible
formation mechanisms (one Au atom substituting for
the Fe atom; one Au atom substituting for one S
atom; two Au atoms substituting for one S2 dimer;
and Au incorporation into an interstitial lattice site)
of gold in a 2 2 2 pyrite supercell (Fe32S64)
investigated by Chen et al. (2014).In most case
telluride coexist with sulphides such as pyrite,
sphalerite, galena and chalcopyrite (Fig 4).
Fig. 2 Bulk FeS2 unit cell (a) and 2 2 2
supercell (b), and schematic diagrams of Au in
pyrite crystal. One Au substituting for one Fe
(Fe31S64Au) (c), one Au substituting for one
S(Fe32S63Au) (d), two Au substituting for a S2
dimer (Fe32S62Au2) (e) and Au in interstitial
lattice site(Fe32S64Au) (f).Source: Chen et al.
(2014)
206
Fig. 3 Mineralogy of Sandoawanzi gold telluride
ore (a) Coexisting petzite, sylvanite and
chalcopyrite in quartz veins in reflected parallel
light); (b) Twins in a calaveritegrain in quartz
vein (reflected polarized light); (c-f) Back-
scattered electron SEM images. (c) Petzite and
sylvanite in association with chalcopyrite. (d)
Sulvanite-hessitesymplectite. (e) Coexisting
krennierite, altaite and chalcopyrite in pyrite-
bearing quartz vein. (f) Coloradoite-petzite
association. Source: Liu et al. (2013).
2.3 Reactive Gangue Minerals
The recovery of gold in cyanidation process is often
accompanied by leaching of other species(sulphides
and sulph-arsenides, mainly those of copper, silver,
antimony and arsenic). These side reactions deplete
free cyanide and oxygen required for gold extraction.
Research has shown that stoichiometric amount of
free cyanide needed for most gold recovery processes
is < 1 % of the total consumed(Petre et al.,
2008).These cyanide- and oxygen-consuming
components are known ascyanicides (e.g. S, Cu,
Zn, Fe, Ni, etc.). They divert the lixiviant into
formation of non-valuable complexes(Bache,
1987;Fraser et al., 1991; Linge, 1995; Hausen, 2000;
 207
Liipo, 2003; Amankwah et al., 2005; Nanthakumar et
al., 2007; Petre et al., 2008; Adams, 2013).
2.4 Adsorption of Gold
During leaching, dissolved gold is sometimes
adsorbed from leach liquor making them unavailable
for concentration byactivated carbon. Gold, adsorbed
by these ore components, report in the tailings. Ore
components capable of adsorbing gold are
carbonaceous materials and other surface active
gangue minerals (e.g., clay, silicates, etc.). When
aurocyanide (Au(CN)2-) is adsorbed by carbonaceous
material present in the ore, it is termed Preg-
robbing(Dunne et al., 2012). This behavior was
detected as early as 1911 by Cowes(Menne, 2003;
Miller et al., 2005). The carbonaceous matter may
occur throughout the ore body or in distinct pods or
veins within a deposit. Preg-robbing capacity varies
widely between carbonaceous ores. Mild preg-
robbing ores may have capacity to adsorb < 1 gAu/t
ore, while extreme preg-robbing ores may have the
capacity to adsorb > 500 g Au/t ore(Dunne et al.,
2012).Miller et al. (2005)Comprehensively reviewed
preg-robbing gold ores. The adsorption process of
carbonaceous material should not be confused with
encapsulation of the gold. The most renowned
examples of carbonaceous ores are the Carlin trend
(Nevada, USA), Ashanti trend (Ghana),
Witwatersrand (South Africa), Muruntau (West
Uzbekistan), Kumtor(Kyrgyzstan), and Macraes
(New Zealand) (Menne, 2003; Miller et al., 2005).
Stenebraten et al. (2000) showed that the presence of
carbonaceous matter in the ore may not necessarily
result in poor gold recovery.Aside carbonaceous
material, minerals (copper-sulphide minerals, clay,
and silicates) can adsorb dissolved gold during
cyanidation (Bowell et al., 1999; Marsden and
House, 2006; Miller et al., 2005; Mohammadnejad et
al., 2014; Saunders, 1990).
2.4.1 Formation of Preg-robbing Gold Ore
The association of gold with carbonaceous matter is
believed to be due to biological redistribution.
However, there are convincing theories relating to the
origin of carbonaceous matter from methane under
severe conditions of pressure and
temperature(Menne, 2003). The carbonaceous
material comes from the solid-state metamorphic
transformation (graphitization) of organic material
originally in contact with the rock. Graphitization
depends on temperature, pressure and type of carbon
precursor (Miller et al., 2005).Carbonaceous matter
207
are usual components of meta-sedimentary rocks that
are often diffused within the mineral matrix.
Research shows that carbon exist in different forms
in the ore, which show different affinities for the
gold-cyanide complex(Stenebraten et al., 2000).The
adsorption ability exhibited by copper-sulfide
minerals, clay and silicates during gold dissolution is
dependent on its surface area and characteristics such
as mineral surface activation (Miller et al., 2005;
Mohammadnejad et al., 2014).
2.5 Gold Passivation during Leaching
During leaching, some ionic species form stable
intermediate adsorbing layers and oxide layers on the
surface of gold mineral(Marsden and House, 2006).
Usually, for reactions where gold passivation occurs,
very low rate of reaction are recorded. Minerals such
as chalcocite, pyrrhotite, gold-telluride, chalcopyrite,
pyrite and stibnite form gold mineral surface
passivation species that retard gold dissolution during
leaching. Intergrowth of the passivating species
results in physical locking of gold mineral for
processing. These precipitates are
formedatfavourablehydrometallurgical conditions
(Climo et al., 2000;Zhang et al., 2009; Kyle et al.,
2012). From principle, passivation increases with pH
to a point of very high alkalinity from which
passivation reduces with further pH increase
(Bagotsky, 2005).
3 Effect of Refractory Gold Ore on
Cyanidation
3.1 Processing of Physically Locked Gold
Since gold mineralization of this type are not by
chemical reactions, physical processes can effectively
render them amenable to cyanidation. Several
research has shown that physically locked gold are
amenable after ultrafine grinding of gold ores (< 11
m) (Fig. 4)(Ellis, 2003). Though the operation is
expensive, Ellis (2003) showed that it was more
economical to some oxidation processes ( Frondel,
1938; Saunders, 1990;Bowell et al., 1999). Not all
physically locked refractory gold ores give a large
recovery improvement after fine milling. Gold locked
in arsenopyrite for example does not achieve the
same gold recovery as gold disseminated in pyrite
due to the smaller gold particle size of the locked
gold (Ellis, 2003). Fig. 4 shows the effect of ultrafine
grinding on gold recovery. Gold in the Kalgoolie
 208
Consolidated Gold Mine (KCGM) ore is not locked
in arsenopyrite.
Fig. 4 Gold Recovery of Arsenopyrite and Pyrite
Ores. Source: Ellis (2003).
3.2 Processing of Chemically Locked Gold
Gold-telluride minerals dissolve more slowly in
cyanide solutions compared with pure gold, resulting
in less efficient gold extraction (Climo et al., 2000;
Henley et al., 2001). The slow dissolution rate in
alkaline cyanide solution has been attributed to the
formation of a passivating film of H2TeO3 that
protect the mineral surface from further oxidation
(Eq. 1). At higher pH (>12), H2TeO3 dissolves to
TeO32- (Eq. 2) (Climo et al., 2000; Zhang et al.,
2009; Kyle et al., 2012).
(1)
(2)
The calaverite leach rate during cyanidation increases
with increasing pH, but the pH increase is limited by
the use of lime as the pH modifier due to its solubility
limit (Kyle et al., 2012). However, most leaching
systems operate between pH 10 and 11. As shown in
Fig. 5, high alkalinity (pH in the range 11 13)
decreases the rate of dissolution (Habashi, 1970;
Marsden and House, 2006).
208
Fig. 5 Effect of pH on the Rate of Dissolution of
Gold and Silver in KCN. Source: Habashi
(1970).
3.3 Processing of Gold Associated with
Reactive Gangue Minerals
Most often, gold is liberated from the ore but a
perceived influence of reactive gangue minerals on
gold processing is a competing consumption of O2
and CN-. It has been postulated for example that
pyrrhotite dissolves in oxygenated alkaline cyanide
solution by oxidation to form dissolved sulphur
species such as SO42, SCN- and Fe(CN)64-,
consuming O2, CN- and alkalinity. The most likely
mechanism of pyrrhotite interference in gold
processing plants involves the precipitation of
dissolved gold on pyrrhotite driven by the oxidation
of surface ferrous hydroxide to ferric hydroxide
(Dunn et al., 1995; Linge, 1995; Petre et al., 2008;
Azizi et al., 2011).
3.4 Processing of Gold Associated with
Adsorbing Minerals
More recently, there has been extensive research
undertaken on the use of thiosulphate as a
replacement for cyanide in preg-robbing ore
treatment with gold thiosulphate complex not readily
adsorbing on active carbon (Dunne et al., 2012). Tan
et al. (2005)showed thatgrinding carbonaceous
materials with the ore is more detrimental than
grinding the ore without carbonaceous matter.
 209
Theyalso showed that, coating of graphite is less than
that of sulphides when ground together with the ore
but the detrimental effect of the graphite is more than
that of sulphides. For mild preg-robbing ores, CIL
circuits can be an effective processing option. Adding
blinding agent, such as kerosene to foul the
carbonaceous material can reduce the preg-robbing
capacity, however care must be taken to ensure that
activity of the activated carbon is maintained(Miller
et al., 2005; Dunne et al., 2012). For other adsorbing
minerals, surface deactivation and control grinding
can reduce their gold adsorbing ability(Miller et al.,
2005).
3.5 Processing of Ores with Passivating
Minerals
Galvanic interaction during leaching has been shown
to improve gold recovery in some refractory ores
(pyrites). However, the presence of minerals such as
sphalerite, chalcocite, stibnite and chalcopyrite in
leaching system cause permanently poor gold
recovery in presence and absence of galvanic
interactions(Azizi et al., 2011). The effect of
sphalerite was attributed to surface obstruction by
passivating film(intermediate products, HS- and/or
Sx2) formed during sphalerite dissolution. Chalcocite
depleted free cyanide in forming copper cyanide and
hydrosulphide. Chalcopyrite, like chalcocite,
consume free cyanide. Hydrosulphide from this
reaction is believed to form passivating film
aroundgold. Stibnite form passivating film of
antimony oxide leading to poor gold
dissolution(Deschenes et al., 2000; Azizi et al.,
2011). Kinetic studies by Petre et al. (2008) argued
that sulphur species affect gold leaching reaction
directly. They observed that leached sulphide ions
passivates the gold surface by forming a passive
Au2S layer. Research shows that, the presence of lead
minerals (lead oxide, lead sulphide and lead sulphite)
in ore improves gold dissolution. The effect
contributed by lead during cyanidation has been
investigated (Deschenes et al., 2000; Azizi et al.,
2011).
4 Changes in Ore Characteristics with
Mining Activities
Various research show variation of ore characteristics
and composition with mining depth (Bache, 1987;
Mason and Nanna, 1988; McKibben, 2005). During
process plant design, inclusion of a particular
209
processing technology (e.g., crushing, grinding,
flotation, oxidation, etc.) is defined by the gold grade
and ore characteristics. Changes in ore characteristics
lead to the closure and re-opening of various mines
with different processing routes. Existing mines need
to introduce new techniques, modify unit operations
and processes in order to register high recoveries of
gold in cases of ore mineralogical variation.Flow
sheets of several mines (Getchell mine, Newmont
Gold Company, etc.) have been modified due to ore
complexity compared with the available technology
(Mason and Nanna, 1988; Kontopoulos and
Stefanakis, 1989; Seymour and Ramadorai, 1989;
Taylor, 2009).
5 Conclusions
This review showed that researchers, institutions,
consulting companies and gold processing companies
have to improve gold extraction techniques as the
mineralogy becomes more complex. Invariably low
gold grade is recently processed as cyanide amenable
portion of gold deposit gets depleted. There is a need
for fundamental studies to aid processing of these
complex ores. This fundamental studies should not be
limited to cyanidation but should include all other
possible economically viable means of extracting
refractory gold mineral. For example, the newly
discovered chemically locked gold at Sandaowanzi,
with its highest gold grade being 20, 000 g/t, needs to
be processed. It is believed that, by creating
conditions, that opposed the concomitant processes
leading to gold deposition, gold, independent of its
complexity, could be extracted. Improved
understanding of the mechanism for extraction can be
determined from the natural mechanism of
deposition.
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