6

Leaching

In the context of gold extraction, leaching is the dissolution of a metal or mineral

in a li qui d. The reaction of primary concern is the dissolution of gold in aqueous
solution, which requires both a complexant and an oxidant to achieve acceptable
leaching rates. Only a limited number of ligands form complexes of sufficient
stability for use in gold extraction processes. Cyanide is universally used beca use
of its relatively low cost and great effectiveness for gold dissol ut io n. Also,
despite sorne concerns over the toxicity of cyanide, it can be applied with little
risk to health and the environ ment. The oxidant most commonly used in cyanide
leaching is oxygen, supplied from air, which contributes to the attractiven s of
the process.
The different processes developed for leaching with cyanide, including agitation
leaching, heap leaching and intensive: cyanidation, and their applications are
reviewed in this chapter.
Non-cyanide reagent schemes have the following potential advantages over
cyanide:
(a) env iro nme nta l p ressures , and in sorne cases restrictions, may make the appli catio
n of cyanide difficult in certain locations;
(b) sorne have faster gold leaching kinetics;
(e) many can be applied in acidic med ia, which may be more suitable for refractory
ore treatme nt ;
(d) sorne are more selective than cyanide for gold and silver over other metals, i.e .
copper.

However, they also have sorne significant disadvantages and none are widely
appli cable .
Chlorine-chloride leaching was applied commercially in the 19th century, but its
use diminished following the introduction ofthe cyanide process in 1889 (Chapter 1 ).
Thiourea, thiosulphate, thiocyanate anda variety of other halide solutions have been
investigated extensively in the laboratory and severa! potential processes have been
developed, but none commercially applied on a large scale. The
260 Leaching [Ch.6

chemistry of these alternative reagent schemes contributes to their lack of commer

cial success and is also discussed.

6.1 CYANIDATION
6.1.1 Chemistry of cyanide solutions
Simple cyanide salts, such as sodium, potassium and calcium cyanides, dissolve and
ionize in water to farm their respective metal cation and free cyanide ions:
(6.1)
The solubilities and relative cyanide content of the different cyanide salts are given in
Table 6.1 [1]. Ali three salts have been used effectively on a commercial scale as
sources of cyanide far leaching. Sodium and potassium cyanide are more readily
soluble than calcium cyanide and are generally available in purer farm, which has
advantages far the handling and distribution of the reagent in leaching systems.
Sodium cyanide is also widely available in solution in sorne regions of the wo rld ,
which avoids the need to dissolve the reagent on site, reducing process requirements.
Thus, the choice of cyanide type depends on the method of application, cost and
availability.

Table 6.1- Properties of simple cyanide compounds [1]

Compound Available cyanide Solubility in water at 25ºC

(%) (g/100 ce)

NaCN 53.1 48
KCN 40.0 50
Ca(CN)z 56.5 Decomposes

Cyanide ions hydrolyse in water to form molecular hydrogen cyanide (HCN) and
hydroxyl (O H- ) ions, with a corresponding increase in pH:
cN- + H2 O ;;:= HCN + o H- (6.2)
Hydrogen cyanide is a weak acid which incompletely dissociates in water as fallows
[2]:
HCN ;;:= H + + CN- ; Ka(25ºC) = 6.2 x 1-
w, pKª = 9.31 (6.3)
0
Fig. 6.1 shows the extent of this dissociation reaction at equilibrium as a function
of pH. At approximately pH 9.3, half of the total cyanide exists as hydrogen
cyanide and half as free cyanide ions. At pH 10.2 more than 90% of the total
cyanide is free cyanide (CN-), while at pH 8.4 over 90% exists as hydrogen
cyanide. This is important because hydrogen cyanide has a relatively high vapour
pressure (100 kPa at 26ºC [3]) and consequently it volatilizes readily at the liquid
surface under ambient
Sec. 6.1] Cyanidation 261

100 .------

80

E
2 60
z
(._)
I HCN CN
e
Q)

:2
e 40
">'
(._)

20

o '----'-----'----'----'------'---':::,._-'---...J
6 7 8 9 10 11 12 13

pH

Fig. 6. 1 - S peciat ion of cyanide and hydrogen cyanide in aqucous solution as a function of pH.

conditions, causing a loss of cyanide from the solution. The rate of volatilization
depends on the hydrogen cyanide concentration (a function of total cyanide
concentration and pH), the surface area and depth of the liquid, temperature and
transport phenomena associated with mixing [3]. As a resu lt, most cyanide leaching
systems are operated ata pH which minimizes cyanide loss, typically above pH 10 ,
although adverse effects may be caused by excessively high pH, as discussed in
section 6.1.4.
Both hydrogen cyanide and free cyanide can be oxidized to cyanate in the
presence of oxygen and under suitably oxidizing co ndition s, as illustrated in the E1,-
pH diagram for the CN- H2O system , given in Fig. 6.2:
4HCN + 3O2 + 2H 2O
4CNO- (6.4)
3C N- + 20 2 + H 2 O 3C NO- + 2O (6.5)
H-
These reactions are undesirable during leaching since they reduce the free cyanide
concentration and the cyanate species formed does not dissolve gold.
Fig. 6.2 indica tes that oxidation should occur spontaneous ly , but in practice
strong oxidizing age nts, such as ozone (0 3) , hydrogen peroxide (H20 2) or hypo
chlorous acid (HO CI) , are requ ired for the react ion to proceed ata significant rate.
262 Leaching [Ch. 6
2.0r--- - -,-- - - --r-- - - - -

1.0 -- --
CNO- _J
1
Eh o 1

-1.0
HCN
[CN) = 10-3 M CN-

-2.0
o 4.0 8.0 12.0 16.0
pH

Fig. 6.2 - E11- pl 1 <liagram for thc CN- H 2O systcm at 25ºC l4J.

In aerated cyanide solutions, the reaction is extremely slow, but can be accelerated
by the action of ultra-violet light, heat, bacteria and catalysts such as titanium
dioxide, zinc oxide and cadmium sulphide [3]. Sorne of these oxidation reactions are
important for the destruction or degradation of cyanide, and are considered in more
detail in Chapter 11.
Free cyanide forms complexes with many metal species, principally the transition
metals, which vary widely in stability and solubility:
M' + + yC N- M(C • (6.6)
N)_)-t ->
for which K [M ' + ]c N- jY/M(C N )_v•-. -\) .
The stability constants of sorne of the more important metal cyanide complexes
are given in Table 6.2. The complexes may be grouped into three main catego rie s,
based on their stability, namely free (HCN, CN- ), weak acid dissociable
(WAD) (log K:,;:;approx. 30) and strong (log K > approx. 30) complexes [3]. These
categories are used widely in the analysis of process solutions since they help to
describe the
behaviour of the cyanide species present, while avoiding the need to provide detailed
analytical information of every cyanide complex present greatly simplifying analyti
cal proced ures . This general grouping is often useful for the evaluation and
optimization of metallurgical performance or when working in environmental
chemistry.
Metal cyanide complexes can form double salts with a variety of cations, e.g. Na ,
K, Ca, NH-1 and many other metal ions. For example, Fe(CN)-;; , which is common
to ali gold Ieaching circuits, forms a large number of salts of varying solubility [5].
The solubility products of a number of these salts are listed in Table 6.3. Of these,
the Fe(III) salt (Fe.¡(Fe (CN) 6 h) is commonly encountered in process effluents,
appear ing as 'prussian bl ue ' precipitate. The formation and solubility of these salts
is an important consideration in effluent disposal and treatment, and is discussed
further in Chapter 11 .
 Sec. 6.1] Cyanidation 263

Table 6.2 - Stabili ty con stants for sele cted metal cyanid e comp le xe s (af ter [5])

Chcm ical fo rmu la Q uant i ty Re ma rks Refere nce

CN (aq) Gº = 41 .2 kcal/mo l 25ºC. I = O [6]

HCN (aq) Gº = 48.6 kcal/mo l [6]
(CNh(g) Gº = 71 . 03 kcal/ mol (6 ]
HOCN (aq) Gº = 28.0 kcal/mo l [6 ]
OCN (aq) Gº = - 23.3 kcal/mo l [6]
HNCO (g) iso- Gº = - 25.66 kcal/mo l (6 ]
HSCN (aq) Gº = 23.3 kcal/ mo l [6]
SCN (aq) Gº = 22. 1 5 kcal/mo l [6]
HCN lo gK 1 = 9 .21 I= O [2]
[Fc(CN) 6] - 4 lo gp6 = 35.4 /=O [2)
¡Fc(CN)6f - lo gP6 = 43.6 /=O [2]
NiCW lo gK 1 = 7.03 /=O (2)
Ni CN- lo gp4 = 30.22 / = 0.5 [2]
¡
NiH CN 4 lo gK 1 1 =5.4 f = 0.5 [2]
Ni H2CN4 lo gK 12 = 4.5 f =0.5 (2]
Ni H.,CN4 lo gK 14 =2.6 / = 0.5 (2]
Ni( CN)- lo g = P6 = 26--27.5 KA c [7,8]
i
CuCN.;- lo gP2 = 16. 26 /=O [ 2]
CuCN- lo gp., = 21.66 !=O [2]
CuCN-] lo gp4 = 23.1 /=O [2]
CuCN (s) pK,11 = 19 .49 [7,8]
Gº = 25.9 kcal/mo l [6]
ZnCN+ lo gK1 =5.3 / = 1.0 [2]
Zn(CN)i (aq) lo gP2 = 11 .07 [2]
Zn(CN)i lo gp., = 16.05 [2]
Zn(CN)-i lo gP4 = 19.62 [21
Zn( CN )- lo gp5 = 20. 1 7 [7.8]
AgCN¡ lo gp2 = 20.48 [2]
AgCN-j lo gp., = 21 .40 [2]
AgCN-] lo gp4 = 20.80 [2]
Ag(OH)CW lo gP1 1 = 1 3. 2 [2]
Ag(CN) (s) pK,p= 15 .66 [21
AuCN¡ lo gP2 = 39.3 (7.81
Au(CN)¡ lo gP2 = 56 [7.81
Gº = 68.3 kcal/mo l [6]
CdCN+ lo gp1 = 6 .01 [2)
CdCN2 (aq) lo gP2 = 1 1. 1 2 [2]
CdCNi lo gp., = 16 .65 [2]
CdCN-¡ lo gP4 = 1 7.92 [2)
Co(CN)- lo gP6 = 1 9.1 [7.8]
i
Co(CN) lo gP6 = 64 [7.8]
lo gP6 = > SO [9)
Co(C N )- H° = 257 kJ/mo l (9]
Co(CN)- /Co(C N E" = - 0.96 V (10]
)-i E"=-0.96V (10 ]
Co(CN)- /Co(C N )-t
KI Fc(CN )6 J-'- lo gK1 =2.49 [11 ]
K2[Fe(CN )6]2- lo gK2 = 3.35 [11]
KH[Fc (CN )6]2- lo gK2 = 5.84 [11l
H[Fc(CN) 6]--' lo gK1 = 4.25 111]
H2[Fc(CN) 6 ]2 lo gK2 = 6.8 [12]
264 Leaching [Ch. 6

Table 6.3 - Solubility products far selected metal cyanide compounds (after [5])

Chemical formula Quantity Reference

Zn(CNh (s) pKr, = 15.5 [2]

Ag(CN) (s) pK,r = 15.66 [2]
Cu2[Fe(C N) 6] (s) pK,r = 17 [13]
Cd 2[Fe(C N) 6] (s) pK, p = 13.4 [12]
K2Cd[Fe(CN) 6] (s) pK, p= 17.1 [12]
K2C u3[Fe(C N) 6] (s) pKr, = 34.3 [13]
Z n2[Fe(C N) 6 ] (s) pK,r = 16.8 [13]
K 2 Z n 1_ [Fe(C N) 6 ] (s) pK,r = 38.5 [13]
KAg 3[Fe(CN)6] (s) pKr, = 19 [13]
Ag.¡[Fe(C N) 6 ] (s) pK,r = 19 [13]
Ni 2[Fe(CN)6] (s) pK,r = 15.89 [7,8]
Co2[Fe(C N) 6] (s) pK,r = 37.32, 15 [7,8]
K4 Ni.¡[Fe(C N) 6h (s) pK, p = 47.5 [12]
K 12 Ni 8 [Fe(C N) 6h (s) pK,p = 113.6 [12]
K 12Cd8[Fe(CN)6h (s) pK,p = 1 21.3 [12]
K2 Ni 3 [Fe(C N) 6h (s) pK,p = 32.56 [12]
K 2Co 3[Fe(C N) 6h (s) = 27.86 [12]
= 45.5 [12]
pKr,
K4Co .¡[Fe(CN) 6 h (s)

pKr,
Co 2[Fe(C N) 6] (s) pK,r = 14.7 [12]
Fe2[Fe(C N) 6] (s) pKsp = 14. 14 [12]
C u3[Fe(CN) <>h (s) pK, p = 24.5 [12]
Cd 1_ [Fe(C N) 6h (s) pK,p = 17.5 [12]
Ag3[Fe(C N) 6 ] (s) pK,p = 18.3 [12]
KC u 111[Fe(C N) 6h (s) pK,r = 74.0 [12]
KC d 10 [Fe(C N) 6h (s) pKr, = 69.0 [12]
Fe[Fe(C N) 6] (aq) logK= 1.3 [7,8]
Fe4[Fe(C N) 6h (s) pK,p = 40.52 [7,8]
N:N i(C N) 4 (s) pK,p = 8.77 [7,8]
Co(CNh (s) pK,p= 10.3 [9]

6.1.2 Gold dissolution

6.1.2.1 Anodic reactions
ln aqueous, alkaline cyanide solution gold is oxidized and dissolve s to form the
Au(I) cyanide complex, Au(CN) 2 , as shown in the Eh-pH diag ram , Fig. 6.3.
The Au(III) cyanide complex, Au(CN)¡, is also formed but the Au(I) complex is
more stable than the Au(III) species by 0.5 V (see sectio n 4.2.2) [14,15]. Far
practical purposes the stoic hio me try of th e dissolution reaction can be assumed to
be:

A u(C N) 2 +e:;= Au + 2CN- (6.7)

far which the Nernst equation is:

Sec. 6.1] Cyanidation 265

3.0 -------------------

Au3+

2.0

>
l.lJ
<O

----
·¡:
; '-
------
e '
o
QJ

1.0
----
----
----
Q.
e
.2
t;
----
:::,
"'O
QJ
---- ---- 2 --------
Au ( CN)----
a:
------ ---
o --
----
------
Au ------------
- 1.0
o 2 4 6 8 10 12 14

pH

F ig . 6.3 - Potc nt i al- p H cquilihrium diagram for thc systcm Au- H10 - CN- at 25ºC. Conccn
trations of ali soluble gold spccics = w- 4 M f 15]

E= - 0.60 + 0.118 pCN + 0.059 log a Au (C N, ) V (6.8)

Cyclic voltammetry has been used to study the mechanism of gold dissolution
(14,16]. Oxidation proceeds in three stages, as indicated by the three peaks in Fig.
6.4. The peak at approximately - 0.4 V probably represents the formation of an
adsorbed intermedia te species, AuCN, which causes temporary passivation of the
gold surface:
266 Leaching [Ch. 6

10 ------- -
11
N
E ,1
8
<( 11
E
6 2 1
· .;;
e
/1 11
"O
a, 4 / 1 1 1
. ..,
e
t
:::,
2
/ U
/
1
1
u / 1
o'----":.....,_,=-=""'"""=-----.. -'
-1.0 O 1.0
Potential (V)

Fig. 6.4-Current versus potcntial curves for thc oxidation of gold in alkalinc cyanidc
solut ion s (after[16)). l, 0.077 M CN- , pH 12;2,0.I MCN,0.1 M O H.

A uC N(ad s) +e;;:= Au + cN- (6.9)

The second peak at approximately 0.3 V is attributed to the complexation reaction
between free cyanide and the adsorbed intermedia te AuCN(a ds l species [14]:
A uC N(ad sl + CN- ;;:=
Au(CN) 2 (6. JO )
In the treatment of ores and concentrates with alkaline cyanide solutions passivation
of gold rarely occurs, even at low cyanide concentrations, probably due to the
presence of low concentrations of heavy meta Is ions (e.g. Pb, Hg) , dissolved from
the feed material, which disrupt the formation of such a passivating layer [16]. This
is discussed further in section 6.1.3.6.
The final peak at 0.6 to O. 7 V is thought to be dueto the formation of an Au( III)
oxide (A u2O 3) layer which passivates the gold surface. Howeve r, such passivation is
unlikely to be a problem in practice because ofthe highly positive potentials required
for this to occur [14-16].

6.1.2.2 Cathodic reactions

In aerated, alkaline cyanide solutions the anodic dissolution reaction [eqn (6.7)] is
accompanied by the cathodic reduction of oxygen. The mechanism of this reaction
has long been under controversy and involves severa! parallel and series cathodic
reactions. Experimental investigation of the stoichiometry of gold dissolution has
shown the major reaction to be [17]:
O 2 + 2H + O + 2e ;;:=H 2 O 2 (6.11)
for which E= 0.69 - 0.059 pH - 0.0295pO2 V.
The hydrogen peroxide formed is a strong oxidizing agent which may take
part in further oxidation reactions:
E°=0.88V (6.12)
Sec. 6. 1] Cyanidation 267

However, the reduction of this species on gold surfaces has been shown to be
kinetically hindered, and the dissolution rate of gold in oxygen-free solutions containing
hydrogen peroxide is very slow [18 , 19] . On the other hand, hydrogen peroxide
decomposes to oxygen and water, as follows:
2H 2O 2:;::=0 2 + 2 H 2 O (6.13)
1t has been demonstrated that as much as 85% of the hydrogen peroxide formed by
oxygen reduction (6.11) diffuses away from the reaction site, with only a small
proportion reduced to hydroxyl ions [18].
Consequently, hydrogen peroxide alone is nota very effective oxidant for use in
gold leaching. The addition of small quantities of hydrogen peroxide can increase the
rate of dissolution slightly, as a result of the increased dissolved oxygen concentra
tion (6.13), but too much may passivate the gold surface by oxide !ayer formation.
Hydrogen peroxide is very effective for the oxidation of sulphides, and has been
used successfully to accelerate low-pressure oxidation kinetics, as discussed further
in section 5.2 [20].
Finally, oxygen may be directly reduced to hydroxide io ns , rather than to H 20 2
(6.11 ):
(6.14)
This reaction requires a large over-potential and is very slow, but occurs in parallel
with (6.11) to a limited extent.

6.1.2.3 Overall dissolution reaction

The overall dissolution of gold in aerated, alkaline cyanide solutions, considering
both the anodic and cathodic half reactions, is most accurately described by the
following reaction equations, which proceed in para lle l:
2Au + 4CN- + 0 2 + 2H 2 O :;::=2 A u (CN) 2 + H 2 O 2 + (6.15)
2OH-
(6.16)
2Au+ 4CN- + H 2O 2 :;::= 2A u(C N) 2 +2OH-
The major reactions are illustrated schematically in Fig. 6.5. The equation proposed
by Elsner (Chapter 1 ):
4A u + 8C N- + O 2 + 2H 2O :;::= 4A u(CN) 2 + 4O H- (6.17)
is stoichiometrically correct, but does not completely describe the cathodic reactions
assoc iated with the dissolution.

6.1.3 Reaction kinetics

The factors affecting the dissolution rate of gold, namely cyanide and oxygen
concentrations, temperature, pH, surface arca of gold exposed, agitation/mass
transport and the presence of other ions in solution, are discussed in detail below.

6.1.3. 1 Cyanide and dissolved oxygen concentration

Considering the general gold dissolution equation (6.15), it is apparent that one mole
of gold requires half a mole of oxygen and two moles of cyanide for dissolution,
depending on the effectiveness of hydrogen peroxide reduction, and the major
268 Leaching [Ch. 6

Salid

Anodic area

2Au + 4CN 2Au (CN )

2
+ 2e

ia

2e

ie

Cathodic area 1

ó 1

, , ---
"-' n
1 1

Fig. 6.5 - Schematic representation of the local corrosion cell ata gold surface in contact with
an oxygen-containing cyanidc solution. (, is the anodic current;ci is thc cathodic curren! [15].

reaction is a two electron process (Fig. 6.5). The rate-limiting condition occurs
when the diffusion rates of cyanide and oxygen are equal, i.e. whichever species has
the slower diffusion rate will provide the rate-limiting factor. At the mixed potential
(Em) the current arising from the cathodic reactions Uc) is equal and opposite to
the anodic current Ua), as shown in Fig. 6.6.
If eqn (4.41) is applied to this system at the rate-limiting condition, where j(C-N )
is equal to j(0 2) , this yields the following:

which simplifies to:

(6.18)

(6.19)
Yalues of the diffusion coefficients, DCN and D0 , , have been estimated at 1.83 x
9 9
1- 0 and 2.76 x 1-0
res
pe
cti (6.20)
ve
ly
[1
7]
.
Th
is
gi
ve
s
th
e
rat
io:
Sec. 6.1] Cyanidation 269

Current

Anodic
U)
Potential

Fig. 6.6 - Simplified schematic diagram of the mixed-potential model for the dissolution of
gold in cyanidc solutions [16].

which has been found to agree closely with observed experimental and practica)
values.

1.50
1
1
0.10 M [CN] ¡o.o, M
1.25 i 1
N 1 1
1 1 1
E 1 1
u 1.00 1 11
<l:
E
1
1
1
I
1
.,.-- 0.0025 M
I 1
1 /
. 0.75 I
1
I
e: I
I
" '
V
>
" 'O
0.21 atm
I1
+ -'
e: 0.50 (02] 1 0.001 M
I
I
:::, I
u 0.25 I
I

,,. /
o -0.7 -0.5 -0.3 -0.1 o 0.1 0.2 0.3
Electrode potential ( V against SH E)

Fig. 6.7 - Electrochemical data for the anodic oxidation of silver and gold and the cathodic
reduction of 0 2 on silver and gold calculated according to mixed kinetic models [23].

Fig. 6.7 shows anodic and cathodic current-potential curves, originally given
for the simple case in Fig 6.6, superimposed on a common current scale (i.e. by
using absolute values for the cathodic and anodic currents) for gold and silver at
various cyanide concentrations. This shows the conditions under which the
dissolution rate is limited by mass transfer of cyanide, oxygen anda combination
ofthe two. In aerated,
270 Leaching [Ch. 6

alkaline cyanide solution the dissolution rate is normally mass transport controlled,
with activation energy values of 8-20 kJ/mol recorded [14, 17], and depends on the
diffusion rate of cyanidc, oxygen or both, to the gold surface [21].
Cyanide concentration is relatively easy to control by the addition of concen
trated cyanide solution, or a solid cyanide compound. Control of the oxidan!
concentration (i.e. dissolved oxygen) is notas easy because of the low solubility of
oxygen in water under atmospheric conditions. Consequently the maximum rate of
gold dissolution for processes that use air to provide oxygen in solution is determined
by the conditions of temperature and pressure that the process operates under. At
sea level and at 25ºC the saturated concentration of dissolved oxygen in solution is
8.2 mg/1. This value decreases with increasing altitude and increasing temperature,
as shown in Fig. 4.13. The corresponding cyanide concentration that gives maximum
dissolution rate of gold at this oxygen concentration is approximately 0.005%, or
0.002 M, c N- , equivalent to 0.01% NaCN. This is supported by practica!
obser vations, as illustrated in Fig. 6.8, where close to maximum gold dissolution
rate (i.e. 3
mg i- 2 - 1) is achieved at 0.02% NaCN [22].
n h

3.5
•
3.0 Gold

1
2.5
.e
"'
1 2.0
- Ol Silver
E 1.5
1.0
a" :'
0.5

o
0.1 0.2 0.3 0.4 0.5

NaCN concentration %

Fig. 6.8 - Effcct of cyanidc conccntration 011 dissolution ratc of gold and silver [22].

In mineral leaching systems, higher cyanide levels may be required due to the
competition of other species for cyanide. An example of this for the leaching of
calcine is given in Fig. 6.9 [24], which shows that increased dissolution rates are
achieved at 0.25% KCN (0.1% or 0.04 M CN- ) compared with iuwer
concentra tions. In practice, cyanide concentrations are usually maintained above
those at which a decrease in extraction is observed, although environmental
concerns often dictate that cyanide concentrations be kept as low as is practically
possible.
The effect of dissolved oxygen concentration on the dissolution rate of gold discs
is illustrated in Fig. 6.10 [25]. In this case, increasing dissolved oxygen concentration
increased the rate of dissolution, up to the maximum of32 mg/1 applied in the tests,
in the presence of excess free cyanide. This effect is further illustrated in Fig. 6.11
for leaching of a gold-bearing calcine [24]. While this shows the effect of dissolved
Sec. 6.1] Cyanidation 271

100 •

80

60
:2
o
l'.l
e 0.25% KCN (- 0. 20% NaCN)
0 0.15% KCN (- 0.12 % NaCN) O 0.05% KCN (- 0.04 % NaCN)
40

20 --- --- ,, ......_ _¡_ _

5 10 15 20 25
Time (h)

Fig. 6.9- Effcct of cyanide concentration on gold recovery from calcine material [24).

oxygen concentration on dissolution rate, it also indicates that similar final gold
ext ract io ns are achieved if leaching times are extended at the lower oxygen
conce ntratio ns. This is an importan! practica! consideration and the cost of increas ing
dissolved oxygen concentration must always be weighed against the cost of providing
extra leaching time .
In practice there are two methods for increasing the dissolved oxygen
conce nt ratio n:
(!) ope rat io n under pressure, using airas the oxidant, or
(2) pure oxygen, oxygen-enriched air, hydrogen peroxide, or another oxygen source
can be used in place of air to supply oxygen to the solution.
Both method s are expensive and can usually only be justified for treatment of ores
containing significan! amounts of oxygen-consuming species.
lt has been suggested that high dissolved oxygen concentrations, for example
above 20 mg/1, may cause passivation ofthe gold surface dueto oxide !ayer
formation [25]. This is considered to be highly unlikely in practice due to the high
solution potential that would be req ui red , and there is Iittle evidence of this from
the majority of research and practica! experience in this area.
A number of alternative oxidants have been proposed to increase gold dissolu tion
kinetics in alk aline cyanide solution, including peroxides of barium , sodium,
potassium, calcium and manganese (each has different solubility and oxygen con tent),
potassium chlorate, potassium permanganate , potassium bichromate and potass i
um ferricyanide. In general the high cost of these reagents prohibits their use and none
of these hav e been applied commercially to any significant extent [26,27].
272 Leaching [Ch. 6

20

15

10
:e
N
E 8
01
E 6

E
e 4
o
· ¡:;
:::,
o
U)

□
□ 4.1 mg/1 oxygen
2
• 8.0
o 14.0
■ 23.0
o L_
o 32.0
_.. _, _, .. ,_

200 400 600 800 1000 2000

Agitation - rpm with 6.1 cm impeller

Fig. 6.1O- Solution ratc of gold disc - cffcct of agitation 125].

6.1.3.2 Temperature
The gold dissolution rate increases with tempe rature , as a result of increased
activities and diffusion rates of reacting species, up to a maximum at approximately
85ºC (Fig. 6.12). Above this tempera tu re the decrease in oxygen solubility
outweighs the benefits of increased ionic activity and diffusion rates. Considering the
example shown in Fig. 6.12, it can be seen that only a 20-25% increase in dissolution
rate is achieved by elevating the temperature from 25ºC to 85ºC. This is supported by
Fig. 6.13, which indicates gold extraction versus time at temperatures between 21ºC
and 45ºC. The high cost associated with such a temperature increase can rarely be
justified for the treatment of low grade materials, and ambient temperatures are
usually applied. However, elevated temperatures have been applied to leaching of
high grade materials (e.g. gravity concentrates). This practice requires that addi tional
free cyanide and oxygen be supp lie d, usually in pressurized systems. This forms the
basis for an intensive cyanidation process, discussed in section 6.1.5.3.

6.1.3.3 pH
The E 11- p H diagram for the gold-cyanide system (Fig. 6.3) indicates that the
electrochemical driving force for disso l ut io n, i.e . the potential difference between
Sec. 6.1] Cyanidation 273

100

26.0 mg/1 oxygen

80 o 14.0
□ 7.5

.t,
>
o 60
u
"O ■ 3.5
o ♦ 2.1
(:J
o 1.0
40

20 --- _._ _._ _._ ..,_ .

o 5 10 15 20 25 30
Time (h)

Fig. 6.11 - Examplc of cyanide cxtraction of gold from calcine: 0.25% KCN [24].

.,
E
¡· :
..; 150
.,
e 140
--2
.,>
"O

]"O
130
120
"O
oCl 110
o..., 100
.e
Cl
·¡¡; 90
o 20 40 60 80 100
Temperature (°C)

Fig. 6.12- Effcct oftcmperaturc on gold dissolution ratc in aeratcd 0.25% KCN solution [28].

the lines representing gold oxidation and oxygen reduction reactions, is maximized
at pH va\ues between approximately 9.O and 9.S. Typically, cyanide leaching is
performed at pH values above 9.4 to prevent excessive loss of cyanide by
hydrolysis, as discussed in section 6.1.1, and the kinetics of gold leaching below pH
9 have little
274 Leaching [Ch. 6

100

80

l
>
oí
o
>
60 • 45ºc
u
e o 30°C
"O
o o 21°c
(.'.)

40

20L_ J_ ...L.._ ...L- _._ .

5 10 15 20 25

Time (h)

Fig. 6.13 - Effect of temperaturc on gold rccovery from calcine material [24].

practica) importance. However, in a few cases, a low pH may be used either to

reduce cyanide concentrations in leach system effluents orto reduce the rate and
extent of other undesirable side reactions, e.g. dissolution of antimony and arsenic
minerals. ln these cases, optimum conditions must be determined by testwork.
The effect of pH on gold dissolution rate above pH 9.5 is small, and depends on
the presence of other solution species and ore constituents, as well as the type of
alkali used for pH modification. In sorne cases, the rate may decrease markedly with
increasing pH, due to an increase in the rate of interfering reactions, such as the
dissolution of sulphides and other reactive species (see section 6.1.4.4). These
effects are generally more severe for calcium hydroxide than either sodium or
potassium hydroxide beca use of the lower solubility of many of the salts formed.
In practice, other process factors usually dictate the actual pH conditions
applied, e.g:
(1) the dissolution rate of other ore constituents, e.g. Cu, Fe, Te, Sb and As
minerals, which can adversely affect gold leaching,
(2) settling properties of the slurry,
(3) slurry viscosity,
(4) cost of pH modification, and
(5) precipitation of solution species, e.g. calcium and iron.
Consequently, the optimum pH for leaching depends on a number of related factors
and must be derived independently for each ore type and leaching system. pH is
considered further in section 6.1.5.
Sec. 6. 1] Cyanidation 275

6.J .3.4 Surface area

The dissolution rate is directly proportional to the exposed surface area of gold and
other particulate factors (section 4.3.5). The exposed surface area is related to the
particle size distribution and liberation characteristics of the feed material, and is
affected by the efficiency of the comminution processes preceding leaching. The rate
generally increases with decreasing particle size, dueto an increase in gold liberation
and/or surface area of gold particles (due to flattening or physical breakage during
grinding). However, this is not always the case and the rate of dissolution from ores
containing cyanicides may decrease with decreasing part .id e size, due to the
increased rate of competing, reagent-consuming side reactions. In such cases, the
optimum particle size is a compromise between gold extraction and cyanide con
sumption. Alternatively, oxidative pretreatment may present the most attractive
processing route for these materials. Particle sizes typically employed in leaching
systems are discussed in section 6.1.5.

6.1.3.5 Agitation
Gold dissolution is usually mass transport controlled under conditions normally
applied for cyanide leaching, and therefore the rate depends on the diffusion !ayer
thickness and mixing characteristics of the bulk solution. lncreasing agitation
increases the dissolution rate up to a maximum, above which agitation has little orno
further benefit. The diffusion layer thickness is minimized by maximizing solution
flowrates past solid particles. In slurry leaching systems this is achieved by mixing
solids and solution with air or by mechanical agitation. Increasing the degree of
agitation in poorly mixed systems may significantly enhance the gold dissolution
rate, as a result of reduced diffusion !ayer thickness and improved homogeneity in
the bulk solution. In well-mixed systems the effect is less significant since the bulk
solution slurry is more homogeneous; it becomes increasingly difficult to reduce the
diffusion layer thickness by agitation alone and increased agitation is often
unjustifiable. This is certainly true of most systems which use modern mechanical
mixing technology, and probably also applies to most air-agitated systems.
In heap, dump, vat or in situ systems the diffusion layer thickness is determined
by solution flowrate past stationary solid particles. Although increasing the solution
flowrate may have a similar effect to that produced by increasing rate of agitation in
slurry systems, i .e. by increasing the mass transport rates of reacting species, the
gold concentration of the leach solution decreases, which may reduce the efficiency
of downstream processes. Consequently, an economic optimum must be established
and this is discussed further in section 6.1.5.

6.J .3.6 Accelerating effect of lead and other metal ions

Certain divalent cations can have a significant effect on the gold dissolution rate.
Trace amounts of lead, mercury, thallium and bismuth are known to depolarize gold
surfaces and prevent or reduce the passivation effect that is observed at - 0.4 Y on
the gold polarization curve: this effect is shown in Fig. 6.14 for mercury and lead
ions [14].
Many ores and concentra tes contain minor amounts of soluble mercury and
lead,
and less commonly bismuth and thallium, which may naturally assist in the leaching
276 Leaching [Ch. 6

0.1 M KOH, 0.1 M KCN

N
==-0.1 M KOH, 0.1 M KCN, and 2 x 10- 6 M Hg(II)
E
10.0 -·-·0.1 M KOH, 0.1 M KCN, and 1 X 10- 6 M Pb(II)
4:
E . n1 r,
/ . I 1

.[ ¡}'
e
V 1
(L)
-.... 5.0 f¡ \ 1
// .
oe
I'¡· \• \
u
:::, // \
oLJ ::::::::::i ::¡ ¡ j_
-0.6 -0.4 -0.2 o 0.2 0.4 0.6

Potential (V)

Fig. 6.14-Effcct of thc addition oflcad and mcrcury ions on thc anodic behaviour of gold
in an alkaline cyanide solution. Beforc each anodic swcep, thc electrode was left under
open circuit conditions for 5 minutes [14].

process. When this is not the case, soluble lead salts may be added to leaching
systems to enhance gold dissolution. The potential disadvantage of such practice is
that any metal species added may report to the final gold product or the tailings.

6.1.4 Behaviour of other minerals in alkaline cyanide solutions

Man y other metals and minerals besides gold also dissolve in dilute alkaline cyanide
solutions. These reactions may consume cyanide and oxygen, as well as producing a
variety of solution species which can reduce the efficiency of gold leaching and
subsequent recovery processes.
Most metal sulphides decompose quite readily in aerated, alkaline cyanide
solution to form metal ions, metal oxides or metal cyanide complexes and various
sulphur-containing species, including thiocyanate, sulphide and thiosulphate ions.
The general reaction for a sulphide containing a divalent metal cation is given as
follows:
2MS+2(x+ l )CN- +0 2 + 2H 2 0 2M(C N)i.2 - x> - +2SCN- + 40 H- (6.21)
An example of this behaviour is the dissolution of pyrite: using the stoichiometry
given in eqn (6.21), it can be shown that an ore containing 1% pyrite would consume
32.6 kg/t NaCN and 2.7 kg/t oxygen, if the pyrite dissolved completely, and if none
of the iron nor sulphur were consumed by species other than cyanide. This cyanide
consumption is a direct reagent cost and may deplete the leach solution of cyanide
necessary for gold dissolution. The oxygen consumption given above is equivalent to
an oxygen mass transfer requirement of l g Oifmin/t solution in a plant with a 24-
hour retention time anda 2:1 liquid:solid ratio.
When sulphide mineral dissolution is significant, severa! pretreatment methods
are available to improve the response to cyanidation. Pre-aeration may be con sidered
for ores containing the more reactive sulphides, such as pyrrhotite and
Sec. 6.1] Cyanidation 277

marcasite, and is considered further in section 5.2. Ores containing significant

amounts of sulphides that cannot be passivated adequately by pre-ae ratio n, and
which result in unacceptable cyanide and/or oxygen consumption, must be treated
by alternative processes, e.g. pressure oxidation, roasting (sections 5.3- 5.8).
Many metal oxides, carbonates, sulphates and other compounds are soluble in
alkaline cyanide solutions, with the solubility dependent on specific solution con
ditions. These minerals gene rally consume smaller quantities of cyanide and oxygen
than sulphides, because the anions produced in solution do not react with cyanide to
any degree, unlike the sulphide species. Consequently, decomposition reactions of
these compounds rarely have a large impact on gold dissolution, although the species
formed may affect precipitation reactions, and overall process efficiency.

6.1.4.1 SilYer minerals

Silver frequently occurs with gold in economically significant quantities and there
fore its behaviour in cyanide solutions is most important. Metallic silver behaves
similarly to gold in aqueous cyanide solution and anodically dissolves as follows:

Ag(C N) 2 +e Ag + 2CN- (6.22)

for which E°= - 0.31 V

The E11- pH diagram for the Ag- C N- H20 system (Fig. 6.15) indicates the region of

2.0

1.0 -- A gCN(s)
Ag+
----
2---
Ag(CN )
Eh o
-- --
---
------
-1.0
Ag [Ag] = ,0- 4 M
[CN) = ,o - 3M

-2.0 -- --- -- .
o 4.0 8.0 12.0 16 .0
pH

Fig. 6. 15 - Eh-pH diagram for the Ag- CN- H2O systcm at 25ºC [4].

predominance of the Ag(I) cyanide complex, and shows that insoluble silver
cyanide, AgCN, is formed at low pH ( < 3.5). The area of predominance of
AgCN(s)
increases significantly as C N- is reduced, for example from 1-0 3
to 1-0
4
M, with
278 Leaching [Ch. 6

important consequences for leaching systems. However, optimum cyanide

concen trations for gold extraction are well in excess of those where such an
insoluble species could form [28].
At very high cyanide concentrations, higher order complexes, such as Ag(C NH
and Ag(C N)-J , may be formed bu_t these are of little practica! importance.
The dissolution of silver has been shown to proceed vía a four-electron mecha
nism, with direct reduction of oxygen to hydroxyl ions [eqn (6.14)], compared to the
two electron path for gold [23]. Oxygen reduction at the silver surface is thought to
involve a mixed diffusion plus charge transfer process, incorporating the adsorption
of oxygen onto the surface. The transfer coefficient for oxygen reduction on silver is
0.25, versus 0.5 on gold. Under conditions typically applied for optima! gold
dissolution, the dissolution rate of silver is significantly slower than gold, as
indicated by the current-potential curves in Fig. 6.7. For example, ata cyanide
concentration of 0.0025 M NaCN and using air to provide oxygen, the dissolution
current density for silver is approximately half that for gold. However, the difference
in dissolution rates are reduced as the cyanide concentration is increased, and Fig.
6.7 shows that the currents for gold and silver approach each other closely at
concentrations in excessof0.J M NaCN.
Consequently, operations which treat ores containing a significant amount of
silver may employ elevated cyanide concentrations to improve silver extractions, and
to overcome any retarding effect on gold dissolution caused by competition for
cyanide. An example of this may be found at Coeur-Rochester (Nevada, USA)
where 0.06-0.08% NaCN is used to treat an ore containing 0.3 g/t gold and 45 g/t
silver. The recoveries of the two metals are 80% and 50% respectively [29]. A
further example of the treatment of high silver ores may be found in section 12.3.1.

6.1.4.2 Copper minerals

Copper minerals dissolve to varying degrees in alkaline cyanide sol utio ns , as
summarized for sorne of the more important mineral species in Table 6.4. This
indicates the solubility of various minerals ground to 100% minus 150 µm and
leached in 0.1 % sodium cyanide solution, expressed as the percentage of the total
weight of mineral dissolved in solution. Copper dissolution is undesirable during
leaching because it can consume cyanide and dissolved oxygen, retard gold dissolu
tion rate, interfere with subsequent recovery processes and contaminate the final
product.
Chalcopyrite is the least soluble of the listed minerals, and is the least soluble
sulphide mineral that is commonly encountered in gold extraction systems.
Chalco cite, bornite, enargite, covellite (although not listed in Table 6.4) and the
copper oxides/carbonates are highly soluble and dissolution of these minerals can
severely affect leaching. While native copper apparently dissolves quite readily in
cyanide solutions, the rate of dissolution is much slower than that of both gold
and silver.
The copper minerals dissolve to form a variety of Cu(I) cyanide complexes,
Cu(CN) 2 , C u(C N)- , C u(CN)-1 , as illustrated by the Eh-pH diagrams for
the
Cu- C N- H 2O system, Fig. 6.16, and for the Cu- S- C N- H 2 O system, Fig. 6.17 [4].
These show the large area of predominance of C u (CN)- under gold dissolution
conditions. However, because the stability constants of the three complexes are
Sec. 6.1] Cyanidation 279

Table 6.4- Solubility of copper minerals in ~ 0.1% NaCN solutions [30]

Mineral Percent total copper dissolved

23ºC 45ºC

Azurite 2CuCO 3 .Cu(O Hh 94.5 100.0

Malachite CuCO 3 .Cu(O H)z 90.2 100.0
Chalcocite Cu2S 90.2 100.0
Copper metal Cu 90.0 100.0
Cuprite C u2O 85.5 100.0
Bornite FeS.2Cu 2S.CuS 70.0 100.0
Ena rgite 3C uS.As 2S5 65.8 75.1
Tetrahedrite 4Cu2S.Sb2S:i 21.9 43.7
Chr ysocolla CuSiO 3 11.8 15.7
Chalcopyrite CuFeS 2 5.6 8.2

2.0 -- -,

11.0 t---- - - - - - -

--
CuO
2
1
o1 Cu20 ---

-- --
---_ -------cu-?-..
-1.0 Cu
[Cu]= 10- 4 M
[CN] = 10- 3 M
- 2.0 '-- - - -'- - - --'-- - - -'----- - _J
o 4.0 8. 12.0 16 .0
0
pH

Fig. 6. 1 6 - E 11- pH diagram fo r th e Cu- CN- H2O syste m at 25ºC [4].

quite close in va l ue , ali are present to sorne extent. The proportions of the different
specie s present in a solution of known pH, tempe rature , copper and cyanide
conce ntration s can be calculated using stability constants for th e various specie s
formed. Fig. 6.18 indica tes the speciatio n of copper cyanide complexes as a function of
pH. The diagram show s only the predom in ant specie s present and does not
 280 Leaching [(

OOr----.-r---r--------.---------,

------
Cu 2+
1.0 CuO
2.
-----
Cu (CN )

-1.0
Cu[Cu] = ,0- 4M
[CN] = 10- 3 M
[S] = ,o - 4 M
-2.0 -- . ,....._ ,
o 4.0 B.O 12 .0 16.0
pH

Fig. 6.17- Eh-pH diagram for the Cu- S- CN- H20 systcm at 2SºC (4].

1.0 ,----.::::::-----;....,..:-::::::----
',,Cu(CN) -

'' '
' .....
0.8
Cu(CN) -
V>
QJ
u
QJ

0.6
o.
QJ

o.
o
2
u
o Cu (CN )

o
e 0.4
· ¡:; A-1
u
A-2
u.

0.2
CuCN

o
2 4 6 8 10
pH

Fig . 6 . 1 8 - Distrihution diagram for copper cyanide complcxes (31].

1
¡
Sec. 6. I] Cyanidation 281

indicate proportions of minor species. Alternatively, an indication of the relative

proportions of the different species present can be obtained by measurement of the
molecular ratio of sodium cyanide to copper in solution. Typically this ratio varíes
between 2.5: l and 3.5:1, which reflects the higher stability of the C u(CN)- complex
under cyanide leaching conditions [30].
The formation of Cu(C N) 2 is favoured at low pH (below 6), under the conditions
specified in Fig. 6.18 and at very low cyanide concentrations, whereas Cu(C N)-J is
the preferred species at high pH and at high cyanide concentrations. This has
important practica! significance since the Cu(CN )-] ion is less readily adsorbed onto
activated carbon. Consequently, high cyanide concentrations can be used to increase
the proportion of this complex and improve the selectivity of gold and silver
recovery from solutions.
The detrimental effect of copper ions on gold dissolution can, in sorne industrial
systems, be attributed to the complications in analysing solutions containing copper
for free cyanide content: during titration with silver nitrate (the standard method of
free cyanide analysis on most plants) a portian ofthe cyanide complexed with copper
is released and complexes with silver to establish a new equilibrium. The extent of
dissociation of the copper complexes depends on the specific solution conditions and
properties. Other interactions with chemical indicators used in the analysis may
further complica te the results obtained. This obviously gives a false indication of
free cyanide concentration available for gold dissolution [32], and copper
concentration must be measured and allowed for in free cyanide determinations.
Copper cyanide complexes have limited ability to dissolve gold. Solutions
containing copper and little orno actual free cyanide (i.e. less than the optimum
for gold dissolution) will have sorne dissolving ability, although ata greatly
reduced rate to that achieved with free cyanide, by virtue of the greater stability
of the gold cyanide complex. The detrimental effect of copper can be avoided by
providing adequate free cyanide in solution to ensure that the gold dissolution
rate is maximized: a molecular ratio of sodium cyanide:copper greater than 4.5:1
must be
maintained for this purpose [30,32], which is equivalent to a mass ratio > 3: l.

6.1.4.3 /ron minerals

Hematite (Fe 2 O3 ) , magnetite (Fe 3O4) , goethite (FeOOH), siderite (FeC O3 ) and
iron silicates are virtually insoluble in alkaline cyanide solutions. Similarly, metallic
iron, which may be introduced to the process as grinding media or used in process
equipment construction, corrodes very slowly, and the reaction accounts for insigni
ficant cyanide and steel consumption in most leaching systems. Iron carbonates, and
other complex carbonate minerals, decompose in low alkalinity solutions ( < pH
10) to sorne extent, but are unreactive at the higher pH values usually applied for
leaching [30].
Oxide minerals that do dissolvé produce the Fe(II) cyanide comp le x, as shown in
Fig. 6.19. This may be further oxidized to iron(III) cyanide, depending on solution
conditions, but the rate of oxidation with dissolved oxygen is slow and stronger
oxidants, such as ozone and hydrogen peroxide, are required for this to proceed
rapidly. The preferred complex coordination number is 6 and both the iron(II) and
iron(III) complexes are very stable, as indicated in Table 6.2. The region of
282 Leaching [Ch. 6

2.0

Fe3+Fe(CN)t

1.0 - - - --
F eO OH FeOOH

Eh o
-------
-1.0
Fe
[Fe) = 1-0 4 M
[CN) = 10- 3 M
-2.0 '-- - - -'- - - - .., .._
o· 4.0 B.O 12.0 16.0

pH

Fig. 6.19 - Eh-pH diagram for the Fc-CN- H 20 systcm at 25ºC [4].

predominance of the iron(III) complex is strongly dependent on free cyanide

concentration and pH, with goethite formed outside this region.
lron sulphides are much more reactive than the oxides and silicates, and most
decompose in alkaline cyanide solutions to form iron cyanide complexes and various
sulphur species. The E11- pH diagram for the Fe-S- CN- H2O system at 25ºC is given
in Fig. 6.20 and for the Fe- As- S- CN- H2O system in Fig. 6.21. The thermodynamic

2.0

Fe(CN) -
Fe3+ FeOOH

1.0 ------ --- FeOOH

---
Eh o

- 1.0
[Fe)= 10- 4 M
[S) = 10- 4 M
[CN) = 10- 3 M
- 2.0 -- --- ---'------'
o 4.0 B. O 12.0 16.0

pH
Fi g. 6.20- Eh - pH diagram for the Fe- S-C N- Hp system at 25ºC [4].

prediction that pyrrhotite is the most reactive iron sulphide in alkaline cyanide
solution is confirmed in practice. Pyrrhotite readily gives up one sulphur atom to
equalize the stoichiometry and reacts with cyanide as follows:
286 Leaching [Ch. 6

(S-;; ) ions have also been detected in cyanide solutions, although generally in lower
concentrations, and their effect on gold leaching is poorly understood.
Thiosulphate species may react further in cyanide solution to form thiocyanate as
follows:
2S20 - + 0 2 + 2CN- = 2SCN- + 2S0- (6.31)
Both thiosulphate and thiocyanate species are themselves capa ble of dissolving
gold, and these reagent schemes are discussed in more detail in sections 6.4 and 6.5.

6.1.4.7 Tellurium minerals

Gold-tellurium minerals (A u_,.TeJ dissolve slowly in alkaline cyanide soluti on,
although the mechanism is poorly· researched and is not well understood.
Tellurium does not form stable complexes with cyanide, as indicated in the E11-pH
diagram for
the Au- Te - C N- H 20 system in Fig. 6.23. In sufficiently oxidizing alkaline cyanide

20
1
1
1

1
Au (CN ) 2
Au (CN ) 2+ 1
+
10 1
HTeO 3
1 TeO
1
Eh 1
1
1
.......
' 1
o Au (CN ) 2 ..j_
+.......
AuT e2 (s) '-.._
Au + AuT e2 (s)
AuT e ( s)
2

-10
o246810 12 14
pH
Fig. 6.23 - E11- pH stability diagram for thc Au- CN- T c- H 2O systcm at [Au] = [Te] =
1.0 x 10 J M. and [CN] = 5.0 x 1-0 3 M [65] .

solution, gold-tellurides decompose to gold(I) cyanide and tellurate species

(Te O- ), for example [37]:
A uT e 2 + 2C N- + 6H 2 0 A u (CN) 2 + 2Te0 + 12H+ + 9e (6.32)
-j
The dissolution rate of gold-tellurides is significan! but slower than that for native
gold and gold-silver alloys in cyanide solutions (Fig. 6.24), and leaching rates vary
for the different minerals, with leaching time requirements in excess of 14 days in
sorne cases (depending on particle size) [36,37]. Leaching rates can be incre ased,
often substantially, by fine grinding and by modifying solution conditions to
optimize
Sec. 6. 1] Cyanidation 289

100

e:
o
·¡;
u
50
.X,
'O
o(:J

OL_.
_.,1. -'------'------ --- -

0.01 0.1 1.0 10 100

P(mm)
Particle
80 size

Fig. 6.25 - Schcmatic illustration of rclationship hetwccn particle size (Px 11) and gold
cxtraction. (a) Gold fine dispersed in a non-porous matrix. Grinding required (Witwatersrand t
ypc) . (b) Gold located in cracks and fissures of rock st ructurc . sorne degrcc of lihcration achieved
at coarsc sizcs (western USA oxidized ore type).

pH modification. Alkali, required for slurry pH modification and control, must

always be added before cyanide addition to provide protective alkalinity which
prevents excessive loss of cyanide by hydrolysis. Most leaching systems operate
between pH 9.5 and pH 11.5. Staged-addition of alkali may be required throughout
the leaching circuit to maintain the desired operating pH, particularly when treating
alkali-consuming materials. pH control is achieved by manual or automatic (on-line)
measurement at various stages in the process.
Cyanide. Cyanide may be added to agitated leaching systems either prior to leaching
ci rcu it, i.e . during grinding, or into the first stage of le ach ing . Subsequent reagent
additions can be made into later stages of leaching to maintain or boost cyanide
concentrations to maximize gold dissolution. Cyanide concentrations are usually
monitored by manual titration techniques, or less commonly by on-line cyanide
analysers, based on titrimetric, colorimetric, potentiometric and ion-specific electrode
techniques.
Oxygen. Oxygen is typically introduced into leaching systems as air, either
sparged into tanks as the primary method of agitation, or supplied purely for
290 Leaching [Ch. 6

aeration. In either case, crude sparging systems are usually sufficient to provide
satisfactory bubble dispersion and to ensure that adequate dissolved oxygen concen
trations are maintained. Opinions vary on the best method of introducing air int o
leach tanks, which include sparging of air:
(a) into the bottom of the tank (single or multiple addition points) ,
(b) into the top of the tank using draught tube systems for dis pe rsio n, or
(c) down the agitator shaft.
The optimum sparging system depends on the geometry of the leach ta nk s. For
e xa mp le , conical-bottomed pachucas with single sparging points (common South
African practice prior to about 1980) and flat-bottomed leach tanks with mu ltipl e
sparging points, or simple down-the-agitator-shaft addition have ali been used.
In a few cases , particularly when treating ores which contain oxygen-consum in g
minerals, pure oxygen (42) or hydrogen peroxide [20) has been added to incre ase
dissolved oxygen concentrations above those attainable with simple air spargin g
systems.
Residence time. Residence time requirmeents vary depending on the le achin g
characteristics of the material treated, and must be determined by testwo rk.
Leaching times applied in practice vary from a few hours to severa) da ys . Le achin
g is usually performed in 4-10 stages, with the individual stage volume and number
of stages used dependent on the slurry flow rate , required residence time and
efficiency of mixing equipment used.
Counter-current leaching. Leaching efficiency can be enhanced by the appli
cation of Le Chatelier's principie: in summary, the Iower the concentration of gold in
solution, the greater the driving force for gold dissolution to occur. This can be
applied in practice by performing intermediate solid-liquid separation steps dur in g
Ieaching to remove high grade gold solutions, and re-diluting the solids with fresh, lower
grade leach solution. Successful applications of this principie are at the Pin son,
Chimney Creek (Nevada, USA) and East Driefontein (South Africa) plants (see
sections 12.2.1 and 12.2.5), and at many other operations (43,44).
On man y operating gold plants there is often an increase in gold dissolution when
a leach slurry is transferred from one type of process equipment to another (i.e .
between Ieach tanks, thickeners, filters, pumps and pipeli nes) , which is illust rated in
Fi g. 6.26. This is explained by the different mixing mechanisms in the diffe rent
equipment, coupled with other factors, such as changes in slurry percent solids and in
solution composition.

6.1.5.2 Heap leaching

Heap Ieaching is a low-cost method suitable for treatment of low-grade mat e rials
which do not justify the higher costs of grinding and agitation Ieaching. O res can be
treated either at a run of mine size or as crushed mate rial , with the optimum size
determined as a trade off between gold recovery and crushing costs. Materials
handling requirements may also play a role in optimizing particle size for heap
leaching since large particles may be difficult to transport by sorne conveyor systems,
an important factor where this presents the most efficient method of material
transport.