Minerals Engineering, Vol. 7, No. 10, pp.

1213-1241, 1994
~ ) Copyright ~ 1994 Elsevier Science Ltd
Pergamon Printed in Great Britain. All rights reserved
0892-6875/94 $7.00+0.00
0892-6875(94)00063-8
REVIEW OF GOLD EXTRACTION FROM ORES
S.R. La BROOY, H. G. LINGE'I" and G.S. WALKER*
A.J. Parker Cooperative Research Centre for Hydrometallurgy, Australia
Mineral Science, Murdoch University, Murdoch, Australia, 6150
"1" CSIRO DMP, Curtin University, Bentley, Australia, 6102
.'1: CSIRO DMP, Floreat Park Laboratories, Wembley, Australia, 6014
(Received 15 March 1994," accepted 26 April 1994)
ABSTRACT
Australia is now an important gold producer in the worM. The nature of Australian goM
production is briefly reviewed and the hydrometalhu'gy of goM extraction is considered.
The choice of processing routes for free milling, complex and refi'actoo, ores is discussed.
For free milling ores, cyanidation and recovely by the Carbon-in-Pulp/Carbon-in-Leach
process (CIP/CIL) is the primary and proven treatment process. Copper containing ores
are discussed its some detail as they interfere in the C1P/CIL process. Oxygen consuming
and preg-robbing ores are also described. Five different classes of process options for
pretreating rejS'actory ores are considered in detail. These options include: ultrafine
grinding," acid and alkaline pressure oxidation; and a variety of chemical pretreatments
such as: Activox process, HMC process and Electrolytic oxidation process, h~ Australia,
the two pre-eminent options for refractory gold ore pretreatment ate roasting attd
biooxidation and this development is reported. The trial of pressure cyanidation of
stibnite concentrates at the Golden Spec mine its Australia is described. Pyrolysis, the
Nitrox/Redox process, the Artech/Cashman process and the Caro's acid process have not
gained commercial status so far.
The potential for resin-in-pulp (RIP) to replace CIP/CIL is discussed. The use of cyanide
has generated environmental concerns because of its toxici~ and therefore research on
alternative goM re.covety processes using non-toxic reagents is considered. The key
candidates are: ammoniacal thiosulphate, thiourea and halide solutions. The chemistry
of these le.aching systems is briefly described and proposed flowsheets are referenced.
The future prospect for biohydrometallurgical goM recovely is indicated.
Keywords
Australian gold production; carbon-in-pulp; carbon-in-leach; resin-in-pulp; gold ore
processing; review of gold extraction; free milling gold ore; refractory gold ore; sulphidic
gold ore; arsenopyritic gold ore; gold recovery process; biohydrometallurgical gold
recovery.
INTRODUCTION
Australia is experiencing the third gold boom in its history. In the first gold boom in 1856, Australia
produced 88 tonnes of gold; in the second boom in 1903, 116 tonnes and in 1990 production reached 245
tormes [1]. To put this production into perspective in the world scene: in 1992, Australia ranked third
1213
1214 s. R. LA BROOY e t al .
behind South At'rica and USA and was the dominant producer in its region [2]. Australia' s production
contributes around 12% to the total world production [2].
In Australia, most of the mines, including the largest single operation based on Kalgoorlie' s "super pi t ",
are situated in Western Australia. Western Australian output consistently accounts for about 75% of
Australia' s production [1,2]. The deposits on which these mines are based can be divided into two broad
categories. In the first category are the generally small, low grade, oxidised deposits directly associated
with previously mined discoveries during the period 1890-1910. These are now economic to mine due
to a combination of factors such as: efficiency of current extraction methods such as Carbon-in-Pulp
(CIP)/Carbon-in-Leach (CIL), which can successfully use saline ground water as found in the "out back"
of Australia; use of low cost, open-pit mining rather than underground mining; and finally an adequate
gold price. Figure 1 illustrates a typical open pit operation in which the shaded portions represent lenses
of high-grade primary gold mineralisation.
Oxide ore
T m n s i U o n ore
P r i m a r y s u l p h i d e o ~ e
Fig. 1 Cross section of gold-ore pit
Unfortunately, as the pits grow deeper readily-leached oxidised gold-ore is gradually being replaced by
primary ore that may be refractory, i.e. may not give economically acceptable gold recovery by
conventional cyanidation. Pretreatment of the refractory material will raise processing costs and will need
to be offset by higher gold grades. It is estimated that most of the oxidised ore bodies in this category
will be exhausted within a few years. The surviving operations will need to adopt some form of
refractory ore processing technology for processing the primary sulphide zone.
In the second category of deposits are the "greenfield" discoveries. These result from modern exploration
eflbrts, including remote sensing teclmiques and high resolution aeromagnetic surveys. Many of these
deposits have substantial and proven long-term reserves which will see them operational until at least the
turn of the century. Over the last five years there has been a decline in the number of mines and a
concomitant consolidation of the companies managing and owning the operations. Western Australia' s
proven reserves indicate that the state will remain the major producer of gold in Australia, unless there
is a collapse of the gold price.
This review considers processing options for gold extraction available for use in the "western worl d".
There is little published information about gold processing technology in the former USSR although gold
recovery was apparently based on Resin-in-Pulp (RIP). In South Africa, a small mine is based on RIP
as will be reviewed below.
Gold extraction from ores 1215
CHOI CE OF PROCESSI NG ROUTE
Generally gold ores can be classified as "free mi l l i ng' , "complex" or "refractory", as illustrated in Figure
2. Free milling ores (sized 80% <75 I.tm) give a gold recovery >90% with a conventional 20-30 hours
cyanidation leach. Sufficient cyanide is added to leave a concentration of 100-250 ppm at about pH 10,
by the end of the leach. Ores that do not provide economic gold recovery with conventional cyanidation
are termed refractory. (In this review, ores that give acceptable economic gold recovery onl y with the
use of significantly higher cyanide or oxygen requirements will be referred to as "compl ex' , while the
term "refractory" will be used when enhanced reagent addition still gives incomplete gold recovery).
GOLD ORE PROCESSING
F R E E M I L L I N G C O M P L E X R E F R A C T O R Y
HIGHLY SEMI-
O X I D E SULPHIDE REFRACTORY REFRACTORY
CYANIDE OXYGEN PREG-
CONSUMING CONSUMI NG ROBBING
Fig. 2 Choice of gold processing route
Ores may not respond to conventional cyanidation for three basic reasons. Firstly, in highly refractory
ores, the gold can be locked up in the mineral matrix so that leach reagents are unable to reach it.
Secondly, in complex ores, reactive minerals in the ore can consume the leach reagents in side reactions
and there may be insufficient cyanide and/or oxygen in the pulp to leach the gold. Thirdly, components
of the ore may adsorb or precipitate the dissolved gold cyanide complex so that it is lost from the leach
liquor. Some ores may have contributions from each of these factors, which will influence the processing
strategy. Ore mineralogy determines the degree of refractoriness and can be graded and classified as
shown in Table 1.
TABLE 1 Classification of ore refract ori ness
< 50% recovery Highly refractory
50-80% recovery Moderately refractory
80-90% recovery Mildly refractory
90-100% recovery Non-refractory (Free Milling)
In Australia [3,4], ores from the weathered profile usually contain most of the gold as metallic grains
which can be exposed with normal grinding. Very fine-grained gold can be exposed with ultra-fine
grinding, although the added gold recovery may not be worth the additional processing cost. In oxidised
ore, the gold can be coated by an iron oxide phase which can significantly slow the rate of cyanidation.
Alternatively, gold can be present in an alloy with silver, as electrum, or in a combined chemical form,
e.g. in tellurides such as calverite ( AuTo) or, less often, as aurostibnite (AuSb2), or occasionally as
rnaldonite (Au2Bi). These chemical combinations of gold can also be physically locked within sulphides.
Even when accessible to the leachant, these gold compounds react very slowly with oxygen and cyanide
1216 S. R. LA Bnoov e t al .
so that gold dissolution is incomplete within the standard leaching period, thus reducing the gold recovery.
Primary ores are often refractory because the gold is locked within the sulphide matrix, which needs to
be broken down to expose the gold.
FREE MI LLI NG ORES
These ores make up the bulk of those currently treated. Processing options are shown in Figure 3.
F R E E M I L L I N G S E M I -
NO CRUSH ~ CRUSH
i | \ - GRINOf
I \ / " I " " E C O N C E N T R A T ' O "
I .
/ | / I GRAVITY FLOTATION
, . Y , I C A L / "
. GRAWTY ~ TAILING
- 6 i , - - / TREAT. eNT
AGGLOMERATION ~ f
~% ,% GRAVITY NONE
REG!IND
Fig.3 Gold processing options for free milling and semi-refractory ores
Placer ores are a special case where no pretreatment is required. Classically these has been recovered
by physical methods such as gravity treatment with sluices, or onto blankets. Modern gravity treatment
units such as Knelson [5] or Falcon [6] concentrators, are in use for gold recovery and supplement
gravitational force with centrifugal force to enable capture of finer gold particles. Another physical
process that has been proposed is coal-oil agglomeration [7,8] with suggested application to alluvial ores
as well as other essentially liberated gold.
For chemical recovery routes pretreatment for free milling ores is usually limited to crushing and
grinding, to make the gold accessible to cyanide, without necessarily being totally liberated. The leach
rate and ultimate gold recovery vary to some extent with fineness of grind. Low grade ores are more
likely to be treated by heap leaching [9,10]. The gold needs to be accessible to cyanide solution for
leaching, hence the permeability of the ore, amongst other things, will dictate the degree of ore
preparation required. The lowest processing cost will come with run-of-mine dump leaching. Less
permeable ore requires crushing before heap leaching, while fines may need to be immobilised by
agglomeration with lime, cement [11,12] or polymeric reagents [13] to prevent percolation problems. The
lower capital and operating costs of heap leaching are somewhat offset by lower gold extraction compared
with conventional milling [14], with typical heap leach recoveries of 60-80%. Current heap leach
operations have cut-off grades as low as 0.2 g. t "l [15]. Pregnant run-off from the base of the heap is
generally contacted by activated carbon in columns (CIC) [16] which usually recovers gold efficiently.
Smaller scale operations with saline water may be better treated by vat leaching (partially flooded heap)
as this reduces scaling problems with liquor irrigation.
Gold extraction from ores 1217
The major processing route for free milling ores in Australia, South Africa and North America is agitation
cyanide leaching with gold recovery by CIP/CIL. This practice has displaced zinc cementation, except
in the case of high silver ores, as there is no need for solid-liquid separation, pregnant solution
clarification and deaeration. Ore preparation usually consists of 2-3 stages of crushing and 1 or 2 stages
of SAG or rod and ball milling to produce a product typically 80% <751am. Except when the particle
size of the gold is extremely fine, it is beneficial for leaching to be preceded by a gravity recovery step.
In this way, gold is recovered more cheaply than cyanidation-CIP/CIL, leach circuit residence time is
minimised, and the gold is available for sale with a minimum delay.
Gold recovery with carbon is usually optirnised between pure CIP and CIL, so that there may be typically
1 or 2 leaching stages before the pulp is contacted by carbon [17]. For a given ore there is an optimum
circuit between the extremes of pure CIP and pure CIL. This compromise will be closer to CIP for high
grade/slow leaching ores and closer to pure CIL for low grade/or fast leaching/or preg-robbing ores [18].
Although gold recovery onto carbon was patented as early as 1894 [19] and used at the Youanmi mine
by 1917, there was no practical process to recycle the carbon after recovering the gold until around 1950
[20]. The full CIP process as we now know it, with carbon adsorption, recovery of the gold from the
carbon and recycling the carbon after thermal regeneration was first applied at a small scale at Cripple
Creek around 1951 [21]; then, at larger scale by Homestake in 1973 [22], but CIP did not really take
of f until its widespread use in South Africa in the late 1970's [23].
Some primary sulphide ores are essentially free milling and can be processed similarly to oxide ores, but
head grades are generally higher and often there is a refractory component in the ore. In some cases, the
refractory component may may respond to finer grinding [24,25]. Sometimes, post leaching retreatment
can be used, e.g. produce a gravity concentrate from the leach residue and grind this finer before
recycling to the beginning of the leach process [26].
When reactive sulphides are present in the pulp there is an enhanced oxygen demand. This can be
satisfied by use of compressed air or the addition of stronger oxidants to the leach tanks. Since 1988
around 30 gold plants in Australia have installed pure oxygen addition during leaching [27], while at least
4 have used hydrogen peroxide addition. Pure oxygen addition is also used when enhanced leach kinetics
are able to offset circuit residence time [28] or short-circuiting problems; or, where cyanide or lime
savings cover the cost of oxygen addition [29].
COMPLEX ORES
Complex ores may be characterised by high cyanide or oxygen consumption or preg-robbing behaviour
(Figure 4).
COMPLEX ORES
CYANI DE
C O N S U ME R S
Copper and
reactive
suIphides
OXYG E N
C ON S U ME R S
Reactive
aulphldea
PREG-
ROBBI NG
Carbonaceous,
eulphidee
and clays
Fig. 4 Complex ore classification
1218 S. R. LA BROOy e t al .
Cyanide Consuming Complex Ores
The occurrence of gold in electrum can lead to slower gold leaching kinetics and increased cyanide
consumption. More serious cyanide consumption can arise from the reaction of some oxides or sulphides.
These side-reactions cause excessive reagent consumption which increases the cost of production as well
as decreasing gold recovery. In Australia the presence of copper in ores is a significant problem in some
deposits. Treatment options are illustrated in Figure 5. Complex ores usually contain a range of sulphide
minerals e.g. pyrrhotite (Fe(l_x)S), marcasite (FeS2), covellite (CuS), digenite (Cu 1.8S), chalcocite (Cu2S),
arsenic and antimony sulphides and zinc sulphide. In gold mines with significant copper sulphide
mineralisation (e.g. more than 1%), gold recovery by cyanidation is usually uneconomic and recovery via
a copper flotation concentrate or chemical pretreatment to remove copper may be required.
CYANI DE CONSUMI NG
COMPLEX ORES
/ PRETR EATMENT . ~ ~ . , ~
NO N E FLOTATION PR E-LEACH
, / \ / ' , , , , " - - " I N T E C
DEXTEC
CYMET
- Acid
CYANIDATION O T H E R CONCENTRATE TAIL - NH3
- Br omi ne
- N H 3 / C N " S E L T
CYANIDE/ - Thiosulphate
METAL - T h i o u r w - C o p p e r
RECOVERY - Slrosmell
- 8 c e r e Mn l . Bromine
Vilrokele Discard I f - Chl odne
- C u T s c h l o w T h l o s u l p h a t e
- I o n F i o l a l l o n enough
- I on Exchange g o l d g r a d e
Fig.5 Process options for cyanide consuming complex ores
Copper minerals can consume large quantities of cyanide to give various copper(I) cyanide complexes:
CuCN, Cu(CN)2-, Cu(CN)32-, Cu(CN)43-, depending on the cyanide to copper ratio in solution. Of
these, only Cu(CN)32-and Cu(CN)43- can dissolve gold [30]. In the absence of pretreatments to remove
copper, cyanide and copper recovery may produce sufficient process credits to make treatment economic
[31-36]. However, copper(II) minerals oxidise an equivalent amount of cyanide to cyanate (CNO-), only
half of which can be recovered as cyanide. Hence, even with cyanide recovery, there can still be
considerable cyanide losses. The only currently installed process for cyanide recovery is the Sceresini
process. In this process, copper cyanide is loaded onto carbon ahead of significant gold dissolution to
be recovered as copper sulphate or sulphide with cyanide regeneration [31]. Alternative processes, such
as the CuTech process [32] offer potential copper and cyanide recovery, but have not been used
commercially to date. The Vitrokele TM process has also been considered for cyanide recovery by loading
copper cyanide complexes from the barren leached pulp onto special ion exchange resins [33], followed
by cyanide and some further gold recovery. Alternatively ion flotation [37,38] or ion exchange resins
[39,40] have been suggested for selective gold recovery in the presence of copper cyanide complexes.
Generally the most economical approach for sulphide ores has been to produce a gold-copper flotation
concentrate for metal recovery by smelting [41]. In some cases, the feed material may benefit from
controlled potential sulphidisation [42-44] which can produce an acceptable copper grade for smelters.
However, the copper grade requirement is likely to lead to reduced gold recovery, so that the float tail
may well contain too much gold to be discarded without further treatment [41].
Gold extraction from ores 1219
Ammonia-cyanide [45-47], bromine [48], thiosulphate [49] and thiourea [50,51] have all been suggested
as alternative reagents for gold dissolution in the presence of copper minerals. Bromine and thiosulphate
have some limited potential for selective leaching of gold over copper, however thiourea offers little
advantage over cyanide as copper minerals have similar rates of dissolution in cyanide and thiourea. In
practice, ammonia-cyanide is suitable as a leachant for low copper values to obtain reasonably selective
gold recovery with little copper leaching, though gold recovery is often limited to 60-80 % [52]. A plant
in Mauritania currently uses this leach system [53].
An alternative approach is to use an electrolytic preleach, such as the Intec process [54], to remove the
copper minerals prior to cyanidation-CIP/CIL. This option was tried at the Rothsay mine in Western
Australia in 1990 [55].
Most gold processing regions in Australia are arid and mines are often forced to use saline ground water
for gold processing. This water normally contains high concentrations of magnesium. The precipitation
of magnesium hydroxide limits the pH below the pK a of HCN (pK a = 9.5) and cyanide can be lost as
HCN vapour unless excess alkali (lime, caustic) has been added to the pulp. The resulting low pulp
cyanide concentration may decrease gold recovery and has an impact on the production cost because of
the high alkali consumption and the possible requirement to use chemical modifiers to overcome high pulp
viscosity due to the precipitated magnesium hydroxide gel [56].
Oxygen Consumi ng Complex Ores
Reactive sulphides such as pyrrhotite can lead to high oxygen requirements as iron(II) is oxidised to
iron(Ill) and sulphide is oxidised to sulphate. This oxygen demand can be met by the addition of oxidants
[57], such as pure oxygen [29], hydrogen peroxide [58] or calcium peroxide [59]. Oxidant addition can
be controlled by a dissolved oxygen electrode in the first leach tank [58], but there can be problems with
meter calibration particularly with saline process water [60]. Sulphides also react with cyanide to give
thiocyanate [57,61]; and processing options are outlined in Figure 6.
OXYGEN
CONSUMING
J COMPLEX ORES
(Reactive aulphide8) " ~
ALKALINE / AERATION
PRE-OXIDATION
- Ai r / FLOTATION
- Air / Pb(NO3)2
L / / CONCENTRATE ~
CYANIDE LEACH
wi t h :
- air
- o x y g e n
- H2 0 2
- Ca O2
Discard
pyrrhotite
rich
tailing
Fig. 6 Processing options lrbr oxygen consuming complex ores
If the reactive sulphides are barren, then selective flotation after aeration can be employed to reject the
easily oxidised sulphides in the float tail. This approach is used at the Three Mile Hill gold mine, at
Coolgardie in Western Australia [62]. Alternatively, at lower pyrrhotite levels alkaline preaeration may
be sufficient to passivate the pyrrhotite with iron (III) oxide/hydroxide films. These films dissolve more
1220 S.R. LA BROOY e t al .
slowly in cyanide solution than pyrrhotite [63], enabling conventional cyanide leaching to be effective.
Lead and/ or oxidant additions may be beneficial during the preaeration and leaching process [64].
Pr eg- Robbi ng Ores
Another class of complex ores are preg-robbing ores, which can be processed by the options shown in
Fi gure 7.
P R E G - R O B B I N G
C O M P L E X O R E S
C L A Y S
J \
H E A T A C I D
, , , /
C Y A N I D E
L E A C H
- C I L
S U L P H I D E S C A R B O N A C E O U S
C Y A N I D E C H L O R I N E
wi t h: I A
- p r e a e r a t i o n
- hi gh [ N a C N ]
L E A C H
- o x y g e n
- C l L - c y a n i d e + O I L
- b r o mi n e
- c hl or i ne
- ~our e a
Fig.7 Treatment options with preg-robbing ores
Preg-robbing behaviour may arise from natural carbonaceous materials in the ore that may adsorb gold.
The most famous examples are the Carlin ores in the USA where the carbonaceous impurity locks
Au( CN) 2 [65]. Preoxidation of Carlin ore with CI 2 (flash chlorination) deactivates the carbonaceous
materials [66]. Alternatively, roasting or bacterial pretreatment [67] can destroy the preg-robbing
behaviour and gold can be recovered by conventional cyanide, bromine, chlorine or thiourea leaching.
Problems with carbonaceous materials in ores are not as serious in Australia and flash chlorination is not
used. Milder preg-robbing can be reduced by addition of diesel or kerosene to the leach to deactivate the
carbonaceous matter in the ore. However, this procedure affects the Au(CN) 2- adsorption onto CIP/ CIL
carbon and therefore requires cautious application. Kerosene addition has been used at Stawell in
Victoria. Graphitic material in the ores does not have the same gold loading capacity as activated carbon
as it has a much lower surface area. Nevertheless it may typically load up to 40 g. t l of gold [68].
Some clays present in gold ores can also adsorb Au(CN) 2- [69-71]. Clays can also hinder the
cyanidation process through coatings or slimes [70]. Mild preg-robbing behaviour can be reduced by use
of CIL, as the activated carbon may have faster gold loading kinetics that the preg-robbers [18,72]. The
probl em is general; e.g. the cationic thiourea complex is even more susceptible to preg-robbing by clays
than the anionic aurocyanide complex [73].
Preg-robbing can also occur at low cyanide concentrations with some sulphides, e. g pyrrhotite and pyrite
[74]. Under these conditions, metallic gold can cement out onto the sulphide minerals [75]. The problem
can be controlled by increasing cyanide levels and/or making conditions more oxidising with preaeration.
REFRACTORY GOLD ORES
A mineralogical examination of the ore normally suggests reasons for the refractoriness of the ore.
Vaughan [76] identified specific mineralogical techniques, which can be used for specifying ore type and
for location of the gold in the ore. These techniques are listed in Table 2.
Gold extraction from o r e s
TABLE 2 Mineralogical techniques for locating gold in the ores
1221
Technique Comment
Optical Microscopy Suitable for coarse gold ( > 0.5 I.tm).
X-ray Diffraction Identification of free mineral grains.
Scanning Electron Microscopy Elemental analysis.
Electron Microprobe Lower detection limits for gold in
solid solution (10-20 ppm).
Ion Microprobe More sensitive for solid solution gold,
claimed to lppm.
Locked Gold
Gold can be locked in the host mineral in a number of ways.
Physical locking in sulphides, oxides, silicates, etc.
Chemical locking as gold alloys or compounds e.g. electrum, gold tellurides,
(aurostibnite), Au2Bi (maidonite), etc.
Gold substitution in the sulphide lattice e.g. "solid solution" gold [4] in arsenopyrite.
Gold surface passivation due to formation of a chemical layer.
AuSI~
In Australia, arsenopyrite, pyrite and chalcopyrite are the principal primary sulphide minerals locking gold
(or alloyed gold) in refractory ore [77]. The options for processing refractory sulphidic ores are complex
and depend greatly on location and mineralogy. Pretreatment options for dealing with refractory ores are
illustrated in Figure 8 and described in detail in the subsequent sections.
THERMAL TREATMENT:
Roasting
Pyrolysis
PRESSURE OXIDATION:
Acid ] Al kal i ne
CHEMICAL TREATMENT: ~ , ~ " ~ ' ~ ' ~ , . ~ . ,
J BIOLOGICAL I
TREATMENT I
Artech/Cashman Process
Redox/Nitrox Processes
AcUvox Process
Caro's Acid
Electrochemical
f /
PHYSICAL
TREATMENT :
Rne gdnding
Fig.8 General process options for pretreating refractory ores
1222 s. R. LA BRoov e t al .
Physical Pr et r eat ment
The only option in this category is to grind finer, e.g. fine grinding with a conventional miU (100%
< 381.tin) [62], or ultrafine grinding with different types of nfills producing particles with sizes in the
range of 1-20 p.m. There are three types of mills for ultrafine grinding, namely: vibratory mills, stirred
mills and j et mills. Of these, the stirred mills are the most cost-effective in terms of the energy input
required to produce a given grain size [24,25], with main application to semi-refractory materials. The
energy intensive nature of the process generally limits its application to higher grade concentrates rather
than whol e ores. A stirred mill is currently used at Newcrest' s New Celebration operation near
Kalgoorlie in Western Australia. This mill regrinds a refractory pyrite gravity concentrate obtained from
the leach residue which is then recycled to the leach [26].
Chemi cal Pr et r eat ment
A variety of wet-oxidation processes can be used to oxidise metal sulphides. The best known process in
this category is pressure oxidation. High pressure processes are reviewed separately in another section
while processes operating at slightly enhanced pressure are covered in this section. The Nitrox/Redox
processes, Artech/Cashman process, Activox process, Caro' s acid process, HMC pipe reactor process
and electrochemical slurry process all involve acid media to breakdown the sulphide matrix to expose the
gold. As an alternative to neutralisation and cyanide leaching, these processes could be coupled with
leaching under acid conditions with thiourea, chlorine or bromine as lixiviants. However the leach residue
would still have to be neutralised before disposal. The Activox, Nitrox/Redox and the Artech/Cashman
processes have been investigated up to pilot plant level and involve less vigorous oxidising conditions than
those in high pressure oxidation processes. The Activox process uses ultrafine grinding to obtain
sufficient matrix attack under the milder conditions. The Nitrox/Redox processes are based on oxidation
with nitric acid and the Artech/Cashman process is a hydrochloric acid pressure leaching process, in the
presence of calcium ions. The use of Caro' s acid (H2SO5) as an oxidant has been tested at a laboratory
scale to oxidise metal sulphides at atmospheric pressure at 60-80C. Electrochemical processing of
arsenopyrite slurries has been investigated at laboratory level.
Ni t r ox/ Redox Processes
The overall chemistry of the Nitrox/Redox processes is the same but there are differences in the operating
temperatures and pressures [78]. The oxidant in these processes is nitric acid, which is recycled. The
Nitrox process uses soluble calcium nitrate and the Redox process regenerates spent nitric acid with
oxygen. The essential schematic of the flow sheet for the Nitrox/Redox process is shown in Figure 9.
For pyrite and arsenopyrite, the oxidation reactions are as follows:
3 Fe S 2 + 18HNO 3 ~ Fe2(SO4) 3 + Fe(NO3) 3 + 3H2SO 4 + 6 H2 0 + 15 NO
3 FeAsS + 14 HNO 3 + 2 H20 ---, 3 FeAsO4. 2H20 + 3 H2SO 4 + 14 NO
Recycling of the acid involves reoxidation of NO to nitric acid:
2 NO + 02 -.-, 2 NO 2
3 NO 2 + H2 0 - - . 2 HNO 3 + NO
The operating conditions for both processes are around 100-400 kPa, 90-110C and a pH < 1. The
reaction in the pipe reactor is very fast and since the nitric acid is regenerated and recycled, there is a
cost saving. Also, lower oxygen concentrations are involved than in high pressure oxidation because
nitric acid is a more powerful oxidant than oxygen.
Gold extraction from ores
Or e S lu r r y
1223
Fig.9
Pi pe A
React or
Ga s Separat i on
Neut ral i sat i on
, P
C y a n id a tio n I C IP
J Nitric A d d I
Re g e n e r a t i o n
I
I
J
The essential steps of the Ni t rox/ Redox processes
HMC Process
This process is a single stage nitric-acid salt leach process which is carried out at 10(YC and up to 1400
kPa in a pipe reactor [79]. The reactor consists of cheap polyethylene coils encased in concrete in a tank.
The oxidising solution is 10-30% w/ w HNO 3 and 10% w/ w sodium chloride solution. Typical ore
constituents (chalcopyrite, pyrite and arsenopyrite) and gold are solubilised within 1 hour for a fine ( < 50
I.tm) 30-60% w/ w slurry. The gold complex in solution is presumably Au(C1)4- and plates as metallic
gold on carbon particles. The loaded carbon is burnt to recover the gold. High gold recoveries ( > 90 %)
have been claimed for various test ores and the process has been patented in several countries (e.g, Aust.
Pat 580768, 4/2/89); but, there is no known commercial application of this technology.
The Ar t ech/ Cas hman Process
The Artech/Cashman process was developed to treat base metal flue dusts containing arsenic. The process
uses Ca 2+ as a reactant in acidic chloride solution at 110C and 350 kPa. The autoclave is lined with
titanium to prevent corrosion of the reactor by HC1. Operating pH is 1-2 and reaction time is 0. 5-1h [80].
In this environment, arsenic is fixed in a combined arsenic-iron-calcium residue which is claimed to have
environmentally acceptable arsenic retention. The process could therefore be suitable for treating
arsenopyritic gold ore in environmentally sensitive areas. However, doubt has been expressed about the
long term stability of the arsenic-iron-calcium residue due to its conversion to calcium carbonate by
reaction with CO 2 in air releasing the arsenic [81].
The Car o' s Acid Process
The Caro' s acid process [82,83] appears to have been explored only at laboratory scale. The sulphide
is slurried in sulphuric acid and Caro' s acid is introduced as the oxidant . Caro' s acid contains the
species H2SO 5 and H202 and is a source of free oxygen in solution, as expressed in the following
equations:
1224 S. R. LA BROOV et al.
H2SO 5 + H202---. H2SO 4 + H2 0 + 02
2 H202 ~ H2 0 + 02
The pr oduct s o f the oxi dat i on o f the sul phi des are sul phat es and arsenates and some el ement al sul phur.
El e c t r oc he mi c a l Pr oces s i ng o f Or e Sl ur r i es
Met al sul phi de and t el l uri de or e part i cl es are el ect ri cal l y conduct i ng and el ect rochemi cal pr ocessi ng is
t herefore possi bl e [4]. Sul phi de oxi dat i on to ei t her sul phur or sul phat e and gol d t el l uri de oxi dat i on c a n
be descr i bed as fol l ows:
MS ---, M + + S O + e-
MS + 4 H2 0 ---, M + + 5042" n t- 8 H + + 7 e-
AuTe 2 + 4 H2 0 ---, Au + 2 HT e O 2 + 6 H + + 6 e -
A pract i cal process that was put in pl ace in the late 1950' s is t he I nco nickel matte anode pr ocess in
Canada whi ch treated cast anodes o f Ni3S 2 [84]. It is usual l y di ffi cul t t o pr oduce compact ed or cast
el ect rodes f r om ores and direct el ect rol ysi s o f slurries is mor e practical. The mi neral part i cl es can be
suspended to make di rect cont act wi t h an inert feeder el ect rode in the cell or react wi t h a sol ut i on r edox
coupl e, whi ch is cont i nuousl y bei ng regenerat ed at the feeder el ect rode. Exper i ence t o dat e shows that
di rect part i cl e-el ect rode cont act is less effi ci ent than the react i on o f or e part i cl es wi t h sol ut i on r edox
species [77]. Thi s mechani sm is summari sed di agr ammat i cal l y in Fi gur e 10 for an oxi dat i on react i on.
-(
'" ~@
~ - . . . . )
M i n e r a l M i n e r a l I o n d iffu s io n A n o d e F e e d e r
P a r t i d e O x i d a t i o n in e l e c t r o l y t e R e a c t i o n e l e c l r o d e
R e a c t i o n a n d d r c u i t
t o c a t h o d e
Fi g. 10 Anode react i on modes for oxi dat i ve sl urry el ect rol ysi s. O denot es t he oxi dant f or m o f t he
r edox coupl e in sol ut i on and R denot es the reduced f or m o f the r edox coupl e in sol ut i on.
The mai n advant ages o f sl urry el ect rol ysi s are as fol l ows:
The material whi ch is to be reacted can be used in its as recei ved f or m, i.e. as a powder .
The surface area o f t he sl urri ed part i cl es is much great er t han that o f cast el ect rodes. Thi s feat ure
reduces ret ent i on t i me and the capital cost o f the plant.
Gol d ext ract i on from ores 1225
Slurry electrolysis has been applied at a laboratory, pilot plant and plant level involving the following
systems: chalcopyrite (CuFeS2) reduction, pyrolusite (l~-MnO 2) reduction, coal oxidation and chalcopyrite
oxidation [54, 55, 77].
Arsenopyrite slurries have been oxidised with anode-generated ferric sulphate or chlorine in a laboratory
scale diaphragm cell. The estimated power consumption was 2. 9 kWh. kg "1 arsenopyrite. Dissolved
As(III) was deposited as As on the cathode [85]. In this system, there was insufficient oxidising strength
in the anolyte and the slurry retention time was similar to biooxidation [86]. Much faster oxidation rates
have been obtained in salt solution in a membrane cell, producing chlorine at the anode. In this system,
power consumption was increased three fold but the cost of this power can be recovered from the sale
of by-product sodium hydroxide. In addition, all dissolved As was present as As(V) and could therefore
be contained in the same way as the effluent from biooxidation. This strategy could make the slurry
electrolysis of arsenopyrite economically competitive with, but much faster than, biooxidation [87].
Act i vox Process
This process utilises ultra fine grinding as a pretreatment to obtain sulphide dissolution under more
moderate conditions than required for high pressure oxidation. Sulphide concentrates are milled in a
vertical stirred mill to a ds0 of about 5 Izm, at an energy requirement of 50-120 kWh. t -1 of feed. The
"activated" material is leached at temperatures below 100C and oxygen overpressures below 900 kPa,
with a retention time of 0.5-1h. In the process, some sulphur is formed but it does not coat gold or
mineral surfaces as the process operates below the melting point of sulphur (120C). The mild conditions
allow the use of rubber or plastic lined mild steel, or stainless steel plant. Laborat ory tests have given
98-99 % gold recovery from pretreated pyrite/arsenopyrite concentrates [88].
Ther mal Pr et r eat ment
Thermal treatment can be applied to break down the sulphide phase to make gold accessible. In the
presence of oxygen, the sulphide converts to an oxide in a process called roasting. Less commonl y, in
the absence of oxygen, the sulphide transforms into a variety of reaction products and this treatment is
described as pyrolysis. Figure 11 illustrates the process options for thermal pretreatment of refractory
ores or concentrates.
THERMAL TREATMENT
J
ROASTI NG PYROLYSI S
/ \
(whole ore) ~ (concentrate) / \
/
. FLASH FLUI DI SED CI RCULATI NG/ SULFUR
ROASTING BED FLUIDISED / REMOVAL
CYANIDE
LEACH
Fig. 11 Process options for thermal pretreatment of refractory ores
1226 s. R. LA BRooe e t al .
R o a s t i n g
Roasting has been the traditional method of pretreating refractory gold ores or concentrates and is one of
the most cost-effective processing options; but the cost goes up significantly, i f sulphur dioxide stack
emissions must be controlled. For example, at Kalgoorlie in Western Australia, pyritic-gold telluride
concentrates are roasted in circulating fluid bed roasters col~structed by Lurgi GmbH [89], with SO 2
emission from a 200m high stack. Although this practice helps manage SO 2 pollution of the nearby
township [90], the practice would not be permitted in less isolated areas, removing much of the cost
advantage of roasting. In Kalgoorlie, there is a shortage of fresh water and saline ground water is used
in gold processing. The salt content of the concentrate feed for the roaster must be limited to minimise
gold volatilisation and subsequent gold deposition within the roaster, e. g. [91]. For arsenopyritic gol dor e,
roasting gives a variable recovery unless the roaster operation is carefully controlled. A pyritic
concentrate containing 5 % arsenopyrite is roasted by Western Mining Corporation at Windarra in Western
Australia in a single stage, stationary fluid bed roaster [92]. However, with arsenopyrite, there is also
the probl em of ensuring environmentally acceptable disposal of the arsenic oxide by-product; hence
alternative oxidation pretreatments could be more attractive.
The objectives in roasting are [93]:
The destruction of the metal sulphide phase.
The exposure of gold in the sulphide.
The production of a high surface area, high porosity haematite (Fe203) calcine.
Minimisation of the production of reactive constituents in the calcine e.g. pyrrhotite, ferrous
sulphate etc. which could consume reagents.
The fixation of arsenic and sulphur in an environmentally acceptable form.
The two most common types of sulphide ore roasters are the stationary fluid bed and the circulating fluid
bed roaster [90]. Figure 12 shows the essential differences between the two roaster types.
Sl urry
St at i onar y Hot Gas Circulating Hot Ga s
Fluid Bed Cycl one Fluid Bed Cycl one
React or Syst em
To Evaporative . . - . - . . . . . . . . . . , _. . _. _
Ga s Cool er ; . ' - ' . ' - " , ~ : . o . . O o . o
I O o O - o ' ,
i ": ": ": ":
": .: .: .:
: .: .: .:
, o O o , . .
I
o . o , , , o O o 1 , o O o , .
Air Q u e n c h
Roasting Air
To Evaporative
Ga s Cool er
To Cal ci ne
Fluid Bed
Cool e r
Fig. 12 Schematic of a stationary and circulating fluid bed roasters
In the stationary fluid bed roaster, the air flow rate and the ore feed rate are regulated so that the solids
in the reactor are maintained in a uniform fluidised state. Coarse calcine is removed through a fluid seal
at the bottom of the roaster into the calcine quench tank and the of f gases are passed into a cycl one where
the finer calcine particles are recovered. The gas flow in the roaster is relatively low and control of the
temperature and gas composition within the relatively dense bed is difficult. There are pockets of very
high temperature, in which the ore is over-roasted and regions deficient in oxygen. In practice,
conventional roasters are therefore associated with gold encapsulation by fused iron oxides in over-roasted
calcine. Alternatively, the combustion of the sulphide in the ore can be incomplete. Both of these factors
decrease the gold extraction by cyanidation-CIP/CIL.
Gold extraction from ores 1227
In the circulating fluid bed roaster, the cyclone and reactor chamber are integrated and enable a
continuous cycling of the ore in the roasting chamber. This increases the overall turbulence in the roaster
chamber and results in much higher heat and mass transfer rates than in stationary fluid bed roasters. The
gas feed and ore feed rates can be varied independently to optimise the performance of the roaster. The
temperature profi l e is uni form throughout the roasting chamber and cyclone, which enables more precise
control of the roast, eliminating both over-roasting and incomplete combustion of the ore. Current
practice at Kalgoorlie achieves 99.5 % elimination of sulphur from the concentrates, a calcine head grade
of 50 g. r -1 and an overall gold recovery of 94% [90].
Pyri t e roasting is normally carried out in the range 650-700C as a "dead roast". This procedure converts
the pyri t e in stages to haematite (Fe203) which is insoluble in cyanide solution and sufficiently porous to
expose the gold particles. The overall equation for the conversion is"
4 Fe S 2 + 11 02 ~ 2Feo_O 3 + 8 SO 2
but the actual reaction takes place in two stages [94]. Firstly, pyrrhotite (FeS) is formed and the
pyrrhot i t e is then converted to haematite. The sulphur is volatilised as SO 2. The two important
parameters in roasting are the partial pressure of oxygen and the temperature in the roasting chamber [89].
Roasting also decomposes the gold-tellurides in the pyritic concentrates above 450C by the reaction [4]:
AuTe + 0 2 ~ Au + TeO 2
Arsenopyrite roasting can be carried out either as a single stage or two stage roast at about 650C in
which arsenopyrite is ultimately converted to haematite, arsenic trioxide (As203) and SO 2 according to
the overall reaction:
2 FeAsS + 5 02 ---. Fe203 + As203 + 2 SO 2
The arsenic trioxide is cooled and collected as a solid and SO 2 is emitted to the atmosphere. The partial
pressure of oxygen and the temperature in the roasting chamber are again the major process variables
controlling the final products.
Pyrol ysi s
Dry and Coetzee [95] studied the pyrolysis of pyrite and arsenopyrite. Simplified equations for the
transformation of each mineral are as follows:
FeS 2 (solid) + heat --, FeS (solid) + S (gas)
FeAsS (solid) + heat .--. FeS (solid) + As (gas)
These reactions liberate the gold and form triolite (FeS), non-stoichiometric pyrrhotite (FeSll + xl), or both.
The metal sulphides that are produced react with cyanide solution forming ferricyanide-ferrocyanide
species. The consumption of cyanide increases the processing cost unless the metal sulphide can be
stabilised, In an extension of this work at a laboratory scale, the gas atmosphere in the furnace was
controlled to include N 2 and SO 2 [96]. In the presence of N 2 the reaction products were essentially
pyrrhot i t e and arsenic. In the presence of SO 2 the reaction products were essentially pyrrhotite, pyrite
and arsenic trioxide.
Bi ol ogi cal Pret reat ment
Biooxidation is now an accepted technology for the pretreatment of refractory sulphide gold ores which
can be retrofitted to conventional cyanidation-C1P/CIL operations [97]. At the Harbour Lights gold mine
at l.,eonora in Western Australia, arsenopyritic concentrates have been processed since June 1992 at the
rate of 40 t.d -1, using Gencor' s proprietary BIOX technology [86]. Further north, at Wiluna, the same
HE 7-10-B
1228 S. R. LA BRooY e t al .
technology is now used to process 115 t.d -1 pyritic/arsenopyritic concentrate. This BIOX plant is
currently the largest biooxidation operation in Australia [98]. At Gencor' s pressure oxidation plant at
Sao Bento in Brazil, a combined BIOX/pressure oxidation circuit is used. This combination results in
lower processing costs and enabled plant throughput to be increased in stages by taking advantage of the
modular nature of the biooxidation process [99]. Another BIOX plant is under construction in Ghana.
The planned throughput will be 2 Mt . y "l of refractory ore and it is said to be the largest BIOX gold
processing plant in the world [100].
Biooxidation has also been proposed as a pretreatment for carbonaceous preg-robbing ores [101,102] and
is well established as a heap/dump leach technique for copper recovery from chalcopyrite. However, in
the gold industry this option is still under development and may well require an acid recovery system for
the gold. The process options for biological pretreatment are illustrated in Figure 13.
BACTERI AL PREOXIDATION
S
WHOLE ORE FLOTATI ON CONCENTRATE
HEAP AGITATED
TREATMENT TREATMENT
NEUTRALI SATI ON
. THI OUREA CYANI DE LEACH
Fig. 13 Process options for biological pretreatment
Biooxidation involves bacterial attack of the sulphide in aerated slurries at ambient temperatures and
pressure in acidic solution. The bacteria dissolve the sulphide by an exothermic oxidation mechanism in
the pH range 1.0-1.5, according to the general reaction (written for arsenopyrite):
FeAsS + 2.5 H20 + 3.5 02 ~ 0.5 Fe203 + H2SO 4 + H3AsO 4
Various types of bacteria e.g. ThiobacillusferrooxMans and Sulpholobus can be used in the biooxidation
step. The mechanisms operating in biooxidation have recently been reviewed [103], and a detailed
mechanistic study of the biooxidation of arsenopyrite has been published [104]. There is a catalysis of
the oxidation of the sulphide surface with dissolved oxygen, which normally requires high temperature
and pressure in the absence of bacteria. The bacteria regenerate continuously, utilising CO 2 from the air
and nutrients from the solution. The bacteria can be killed by toxins e.g. dissolved Cu, Zn, As, Sb and
Ag; but they can adapt to some degree to these toxins in the pulp.
A major advantage of biooxidation is that for sulphides in which gold is concentrated at grain boundaries
or other preferred sites, only partial oxidation of the sulphide is required. The bacteria preferentially
attack at such sites liberating gold very efficiently. However, this advantage does not apply when gold
is in "solid solution" [4] within the sulphide phase, as is often the case for arsenopyrite [97]. Other
advantages of bacterial oxidation include:
Modular process with easy scale up by adding further tanks.
No atmospheric pollution.
Gold extraction from ores 1229
Disadvantages of bacterial oxidation and considerations i n cyanidation of biooxidised products [105]
include the following:
Slow rate of reaction, e.g. days are required for effective treatment of sulphide concentrates.
Careful temperature control required.
Corrosion due to low pH pulps.
The possibility of carbon deactivation in the CIP section of the plant due to fouling by dissolved
organic residues from the bacterial reaction.
Possible foaming problems.
The relative economics for treating sulphide ores by biooxidation compared to pressure oxidation and
roasting (including the projected cost of SO 2 recovery) have been given for a 100 t.d -1 plant in Table 3,
showing that biooxidation is the cheapest option [97].
TABLE 3 Cost comparison of process options (after [97])
II Biooxidation Pressure Roasting
Capital ($US mill) 3.8 7.5 4.9
Operating Cost 43 43 56
($US/tonne)
Pressure Oxidation Pret reat ment
Process options for high pressure oxidation are illustrated in Figure 14. Whilst the normal route for gold
recovery following pressure oxidation is still cyanidation-CIL/CIP, much research has been carried out
on acid leach systems to avoid the need for pre-leach neutralisation.
PRESSURE TREATMENT
OR E P R E T R E A T M E N T
P R E S S U R E
C Y A N I D A T I O N
J
F L O T A T I O N
ADJ US T CONCE NT RAT I ON OF
BASI C COMP ONE NT S I N ORE
ACI D t~
P R E S S U R E
O X I D A T I O N A L K A L I N E
O X I D A T I O N
N E U T R A L I S A T I O N
Thi our e a L E A C H
Ch l o r i n e Cy a ni de
Br omi ne
T h i o e u l p h a t e
I o d i n e
Fig. 14 Process options for pressure pretreatment-leaching of refractory materials
1230 S. R. LA BROOY et al .
Pressure oxidation of refractory sulphides is an established technology and seven commercial plants have
been built [77]. The technology is mature but it is still regarded a high technology-high capital cost option
[106]. The process is best suited to ores that require complete sulphide destruction.
Aci d Pr essur e Oxi dat i on
Typical operating conditions are temperatures of 170-225C with a retention time of 1-3h in a 4 or 5
compartment autoclave [107]. Operation at around 200C minimises construction cost of autoclaves
[108]. Temperatures need to be above 160C to ensure irreversible oxidation of sulphur to sulphate, as
molten sulphur can occlude gold and consume cyanide in subsequent cyanidation-CIP/CIL . In the
autoclave, pyri t e and arsenopyrite initially dissolve to form ferric, sulphate and arsenate ions which are
transformed by hydrolysis into solids such as scorodite, haematite, basic iron (III) sulphates and jarosites
[107,108].
The rate of reaction is controlled by oxygen mass transfer to the mineral surface. Hence, finer grinding
to increase surface area increases the rate of reaction. Oxygen is blown through the system to increase
turbulence and aid its dissolution. Overall pressures of 1100-3200 kPa are employed with oxygen partial
pressures of 350-700 kPa [107]. Higher oxygen partial pressures would allow more rapid oxidation but
would cause overheating leading to equipment failures, Autoclave pressure vessels are constructed of
carbon steel, protected from chemical attack by a lead or fibreglass reinforced vinyl ester lining. This
lining is itself thermally insulated by layers of acid resistant brick. Exotic titanium based materials are
generally required for internal components wetted by the slurry [109]. Combustion of titanium
components within the autoclave can occur without adequate control of operating conditions. Typical
oxygen utilisation efficiency is around 50-90% depending on how much CO 2 has to be vented [110]. On-
site oxygen generation facilities are generally required. Autogenous operation is possible with > 3 %
sulphide sulphur in the feed [111] but is also dependent on carbonate content, number of pretreatment
stages, pulp density and operating temperature [112]. The organic carbon content of the feed does not
contribute a heat input to the process [112]. Pulp acidity is generally controlled at pH < 2 [110] to
maintain a satisfactory redox potential and prevent excessive precipitation in the autoclaves. Oxidation
of sulphur in the feed to sulphuric acid keeps the pH low. If the sulphur content of the feed is less than
2%, acid has to be recycled to the feed, or fresh acid added [110]. The size of autoclaves is determined
by sulphur oxidation requirements [109]; hence treatment of whole ore is feasible i f the ore does not
respond well to flotation.
Al kal i ne Pressure Oxi dati on
Oxidation under neutral or slightly alkaline conditions can be practised for high carbonate ( > 10% CO32" )
and low sulphur ores ( <2 %) and is used at Barrick' s Mercur plant in Utah, USA [113]. This process
operates at 220C with an oxygen partial pressure of 140-180 kPa and 3300 kPa total pressure and
dissolves pyrite to form iron oxides/hydroxides and sulphuric acid. At Mercur, the acid generated in the
process is neutralised by the carbonate in the ore; thus this process would attract additional reagent costs
in a more general application. The capital cost of the plant for alkaline pressure oxidation is less than
for acid pressure oxidation because stainless steel (rather than titanium) can be used for valves and pipes
within the autoclaves ; however, gold recovery is lower [114], as insoluble iron oxides/hydroxides can
form and coat gold and sulphide mineral surfaces [110].
Pressure Cyani dat i on
Pietsch [ 115] demonstrated that elevated oxygen pressure and increased temperatures during cyanidation
could improve the rate of gold dissolution. However, cyanide decomposes rapidly above 75C which
limits the maximum temperature that can be applied in practice. The reaction can be carried out in an
autoclave or pipe reactor. The technique has been applied to cyanidation of stibnite containing ores or
concentrates, which give poor gold recovery under atmospheric conditions [63]. The problem has been
ascribed to oxygen depletion associated with the formation of antimonites and thioantimonites, with
stibnite decomposition being greater at p H> 10. Pressure cyanidation at pH <10 has been patented for
Gold extraction from ores 1231
gold recovery from stibnite concentrates [116]. This process gave 90% gold recovery from a stibnite
concentrate but lower recovery from an arsenic rich middling. Pressure cyanidation of stibnite
concentrate, using a rotating cylindrical contactor, was practiced at the Blue Spec mine in Western
Australia but failed to gain commercial status [117]. Laboratory investigations showed that pressure
cyanidation of stibnite concentrates was able to recover the free gold, but recovery of encapsulated gold
was only possible after destruction of the stibnite [117].
GOLD EXTRACTI ON PROCESSES
Cyani de
The normal gold recovery step involves alkaline cyanidation-CIP/CIL. This process requires
neutralisation of feed from biooxidation or acid pressure oxidation. Cyanidation-CIP/CIL was covered
in detail earlier in this review.
Use of the RIP process in the "western world" is in its infancy. RIP has only been used at the Golden
Jubilee mine in South Africa, where the ore was heavily contaminated with natural humates and fulvates
which completely fouled CIP/CIL carbon [118]. The potential of RIP as a replacement for CIP/CIL has
been extensively reviewed by Fleming [119,120]. The main advantages of resins are: less sensitivity to
organics, high adsorption rate, low temperature elution and promise of gold specificity under certain
conditions for resins still under development. The disadvantages of resins include: smaller particle sizes
requiring finer screens, possible sensitivity to osmotic shock and rapid in-pulp wear of certain resins.
Resins are also three to five times more expensive than activated carbon on a mass for mass basis. In
view of faster kinetics and more favourable equilibrium loadings a resin plant is likely to be operated
much closer to equilibrium than activated carbon, requiring tighter operating control of the plant [120].
The prospect for the future application of RIP is still being debated [120,121]; interestingly, RIP
technology is reported to have had widespread use in the former USSR [122,123].
Cyanide has generated environmental concerns because of its toxicity and an alternative non-toxic alkaline
process that has been considered is the ammoniacal thiosulphate leaching of gold. There are also a
number of possible acid gold recovery options. The technology is generally immature, but could eliminate
the neutralisation costs. The best researched acidic options include thiourea and halide ions.
Ammoni acal Thi osul phat e
Gold forms a stable anionic complex with thiosulphate according to the following reaction:
2 Au + 0.5 02 + 4 $2032" + H20 ~ 2 Au($203)23" + 2 OH-
Alkaline solutions are used to prevent the decomposition of thiosulphate by acid although the gold
thiosulphate complex is quite stable once it has formed. The first reported use for thiosulphate for gold
leaching was part of the von Patera process for silver recovery. In this process, ores were given a
chloridising roast and then leached with sodium thiosulphate [49]. It was subsequently found that copper
ion accelerated the dissolution rate of gold twenty fold. Problems are encountered due to the formation
of a copper sulphide layer on the gold [124], which can be overcome by pressure leaching in an
ammonium sulphate solution. In 1979, Berezowsky and Sefton [125] revived interest in an atmospheric
ammoniacal leach process for gold recovery. There was further improvement by Kerley [126,127], who
patented the use of sulphite to complex sulphide ions in solution to prevent formation of metal sulphide
films on the surface of exposed gold.
There have been several laboratory scale investigations into the use of thiosulphate to leach gold from
various types of ores [49,128-130]. Recent electrochemical studies have supported the mechanism
proposed by Cao et al. [130], that the role of ammonia is to provide a gold-amine intermediate complex,
which is then stabilised by conversion to the gold thiosuiphate complex, while copper(II) amine is the
1232 S. R. LA BRoov et al .
oxidation catalyst [131]. Cao et al. [130] report that the gold(I) amine complex, Au(NH3)2+, is the
thermodynamically more stable species above pH 9, however their tests showed little gold dissolution at
pH 10 in the absence of thiosulphate. This is consistent with the slow dissolution kinetics reported for
the gold amine complex under ambient conditions [132].
Little data is available on the recovery of gold thiosulphate species from solution. Thermodynamic
considerations suggest that gold thiosulphate adsorption onto carbon should be similar to gold cyanide
which suggests that a CIP type process may be applicable [133]. However, Hu and Gong [128] were only
able to achieve limited gold recovery onto activated carbon; they recommended cementation onto zinc as
more effective.
Ammoni a
The gold(I) amine complex, Au(NH3)2 + , is thermodynamically stable at pH >9 and Han and Meng [132]
proposed pressure leaching with ammonia at elevated temperatures as a means of overcoming the slow
leaching kinetics under ambient conditions.
Esoteric Reagents
A new, unidentified gold complexing reagent CSUT (1) has been demonstrated [134]. The reagent can
be used with a range of oxidants, with optimum leaching pH 9-10, but the reaction rate is faster than in
cyanide solution. The gold complex can be recovered on carbon, Magchar and by zinc precipitation.
It has been shown that different heterotrophic bacteria can leach gold from oxide ore. Gold is oxidised
and complexed with microbial peroxides and gold complexing microbial metabolites e.g. amino acids,
peptides, proteins and nucleic acids. The best results are obtained with bacillus strains which are active
in slightly alkaline solutions (pH 8-10) since the gold complexes are unstable in acid solution. The
bacteria leach gold more efficiently when grown in the presence of the ore and the process can be
economically attractive when carbonaceous ore impurities are available as nutrients. The present day
status and future prospects of the biohydrometallurgy of gold has recently been reviewed by Groudev and
Groudeva [135].
Thi our ea
Acidic thiourea solutions (pH 1-2) can be used as a solvent for gold. The anodic reaction follows the
equation:
Au + 2 CS(NH2) 2 = Au(CS[NH2]2)2 + + e-
E h values of 0.4-0.6V are required for significant rates of gold dissolution [136-138] and the gold is
usually oxidised with ferric ion in the leach pulp. Although this reagent has low acute toxicity and the
gold dissolution is rapid, commercial adoption of the process has been hindered by three factors: thiourea
is more expensive than cyanide, consumption is high and the gold recovery step requires more
development. Reagent consumption is high because thiourea is readily oxidised in solution to formamidine
disulphide which does not complex gold. Addition of SO 2 or of sulphites has been proposed to reduce
tbiourea consumption [139,140]. More recently, a modified thiourea leaching process has been developed
with selective complexation of ferric ions to control the E h and minimise thiourea consumption [138].
To date the best known plant application of thiourea has been due to its tolerance to stibnite. New
England Antimony Mines in New South Wales (Australia) recovered 50-80 % of the gold from a stibnite
concentrate via a thiourea leach followed by gold recovery onto activated carbon [141]. It has been
reported that gold can be recovered from carbon by stripping with an acid thiourea solution doped with
an organic solvent such as butanol [139,140]. Under highly acid conditions, in the presence of free
thiourea, gold loads as the gold thiourea complex. Unfortunately, thiourea is also adsorbed onto the
Gold extraction from ores 1233
carbon [120]. In the absence of free thiourea, gold is more likely to be partly reduced to gold metal by
the activated carbon. Gol d recovery onto strong base cation exchange resin, followed by elution with
ammoni um thiosulphate solution has also been proposed, but more recent studies suggest that there could
be problems with both resin and carbon poisoning by elemental sulphur [143]. Cementation onto steel
turnings activated by washing with nitric acid, has also been suggested as a faster recovery process [144].
Halides
The halides, C1, Br, and I in appropriate solutions have been used for many years to extract gold [145].
A generalised anodic reaction for gold dissolution with the halide ion X- is as follows:
Au + n X- --.+ AuXn (n-m)" + m e-
The accompanying cathodic reaction is as follows:
Chlorination (pH i): major oxidant, chlorine:
CI 2 + 2 e- ---, 2 C1-
Chlorination (pH 5): major oxidant, hypochlorous acid;
HOCI + 2 e - ---, CI- + OH-
Bromination (pH i-6): major oxidant, hypobromous acid;
HOBr + 2 e - ---, Br- + OH-
Iodination (pH 1): major oxidant, triiodide ion;
I3- + 2 e - ~ 3I -
The use of halide systems for gold dissolution predates cyanidation. Historically, chlorination was
practiced in Australia as early as 1891 [20]. However, halide systems are currently limited to analytical
applications, where the speed of dissolution and capacity for simultaneous sulphide destruction are more
important than reagent consumption.
Chlorination rates are favoured by low pH, high chloride and chlorine levels, increased temperature and
high ore surface area [146]. Gold dissolution with chlorine is much faster than with cyanide [142].
However, even low concentrations of sulphides e.g. 0.5 %, or other reactive components in the ore, can
make reagent consumption excessive and can reduce AuCI 4" back to metallic gold. In addition, an acidic
system increases corrosion in the plant resulting in higher costs. A price advantage over the cost of
cyanide might be achieved by electrolytic production of chlorine from ground water brines when natural
waters are saline. Such a process has been proposed for in-situ gold extraction [147].
Historically AuCI 4- was recovered as metallic gold on carbon or charcoal [20], and the loaded charcoal
was then burnt to yield the gold. Hence high gold loadings would be required on the carbon to make the
process economically viable. This would tend to rule out in-pulp recovery as there would be the danger
of fine gold being abraded of f the carbon surface [143] and lost to the tailing. An elution process that
would permit recycling of the carbon has yet to be demonstrated. It should be feasible to treat the loaded
carbon in a cyanidation-CIL process. Gold can also be recovered as AuCI 4- on anion exchange resins,
which should permit in-pulp recovery; but once again, the stripping process has yet to be fully
demonstrated, to confi rm that the resins can tolerate the oxidising conditions required to keep AuCI 4- in
solution [ 143]. Polyacrylic ester adsorbents show promise of greater stability under oxidising conditions
than ion exchange resins [143]. Gold can be readily recovered from clarified solution by chemical
reduction.
1234 S.R. LA BRoov e t al .
Several investigators have studied the use of bromine [148]. Currently, the most appropriate source of
bromine appears to be the N-halo hydantoins. A commercial grade of hydantoins are the Geobrome range
of reagents e.g. dibromodimethylhydantoin (Geobrome 55). These reagents have been evaluated and the
performance of the cheapest reagent (Geobrome 3400, which contains about 34 % of bromine as Br2) has
been studied in detail [148]. These reagents are generally denoted as Br2(DMH) and are a convenient and
stable source of hypobromous acid according to the following reaction:
Br2(DMH ) + 2 H20 -+ 2 HOBr + H2(DMH )
The advantages claimed for this system are: rapid extraction, non-toxicity and operation in the range pH
1-6. However, the gold surface can passivate in neutral solution. Commercial use of this reagent has
not yet been reported. The form of the gold-bromine complex loading onto activated carbon is sensitive
to the free bromine concentration [149], with less metallic gold in the presence of free bromine. Loading
of AuBr 4- onto anion exchange resin is reported to be followed by reduction to metallic gold, with
oxidative degradation of the resin as with the gold-chloride complex [150].
Of the halogens, the gold iodide complexes are the most stable in aqueous solutions. Furthermore, iodine
solution does not normally oxidise metal sulphides such as chalcocite and pyrrhotite avoiding excessive
reagent consumption in a potential gold processing circuit [145]. Solid iodine reacts with iodide in
aqueous solution to form the triiodide:
I2(aq ) + I" --, 13 -
An in-situ leaching process based on the oxidation with triiodide has been patented [151]. The gold
leaching rates in iodide solutions are much faster than conventional cyanidation and a conceptual flow
sheet for recovering gold from ores by iodide leaching has been published [145]. This scheme includes
steps for gold and reagent recovery. However, there has been no economic evaluation or commercial
application of this flowsheet to date.
CONCLUSIONS
Cyanidation-CIP/CIL remains unchallenged as the premier process for gold extraction from ores although
the use of cyanide has generated environmental concerns because of its toxicity. There is no immediate
prospect for RIP to replace CIP/CIL. It is possible that the RIP technology from the former USSR can
be utilised in the future. In addition, resins are likely to find niche applications in problem plants
containing high organic impurity loads; or, in the separation of different metal cyanides; or, in gold plants
based on heap leaching.
For more complex ores, ammonia cyanide leaching and oxygen addition offer the best prospects for
minimising the processing cost of these resources by cyanidation with gold recovery via carbon
adsorption. Alternatively, an electrolytic preleach such as the Intec process, has been trialed to remove
copper prior to cyanidation-CIP/CIL.
The choice of pretreatment option for refractory ores depends greatly on location and legislative controls.
Roasting without sulphur dioxide recovery is the cheapest option; but with more stringent environmental
controls the cost differential between the options narrows. In Australia, roasting is still used in an arid
and isolated environment to treat the output from the largest single mining operation in the country. High
pressure leaching is a mature high technology processing option used particularly in North America. The
Nitrox/Redox processes and the Artech/Cashman process have been trialed commercially in various
countries but have not displaced high pressure oxidation. The South African Biox process is becoming
more and more widely accepted internationally and Australia has currently the largest operating plant
based on this technology. Niche applications have been found tbr options based on ultrafine grinding.
There appears to be no further development of the Caro' s acid process or commercial application of the
HMC process. An electrolytic oxidation process for recovering gold from arsenopyritic concentrate has
Gol d ext r act i on f r om or es 1235
been tested on a laboratory scale and could be competitive with existing options depending on mine
locality.
Alternative gold recovery system have been widely researched but have not displaced eyanidation-
CIP/CIL. The new biohydrometallurgical routes for gold extraction could well be the environmentally
friendly technology of the future and are certainly worth watching.
ACKNOWLEDGEMENTS
We thank Warren Jones for drawing some of the Figures; Gary Johnson and Dave Muir for valuable
discussion and Jim Avraamides, Ann Bax and Jeff Duma for constructive criticisms of the draft of this
review. This work has been supported under the Australian Government's Cooperative Research Centres
Program. This support is gratefully acknowledged.
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