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Gold
Gold
Gold
Complexformation: Au
+
+2CN
[Au(CN)
2
]
Reduction: O
2
+2H
2
O +2e
H
2
O
2
+2OH
O
2
+2H
2
O +4e
4OH
Overall reactions:
2Au +4CN
+O
2
+2H
2
O
2[Au(CN)
2
]
+H
2
O
2
+2OH
4Au +8CN
+O
2
+2H
2
O 4[Au(CN)
2
]
+4OH
6
The electrochemical nature of this process has The electrochemical nature of this process has
been demonstrated by embedding a small gold been demonstrated by embedding a small gold
sphere in a KCN gel to which air was introduced sphere in a KCN gel to which air was introduced
from one direction. from one direction.
It was found that the gold corroded at the It was found that the gold corroded at the
surface far away from the air flow, i.e., an surface far away from the air flow, i.e., an
oxygen concentration cell was formed around oxygen concentration cell was formed around
the sphere: The surface less exposed to oxygen the sphere: The surface less exposed to oxygen
acted as anode while the surface in direct acted as anode while the surface in direct
contact with oxygen acted as cathode. contact with oxygen acted as cathode.
Stoichiometry of cyanidation:
A) Consumption of cyanide
Amount of gold
dissolved
Observed
consumption of
cyanide
Time
[hours]
mg
equivalent
(x 10
3
)
mg
moles
(x 10
3
)
Molar ratio
[KCN/Au]
0.5
1.0
3.0
7.0
10.0
0.96
2.01
7.49
15.91
18.77
4.86
10.2
38.0
80.9
95.1
0.62
1.26
4.94
10.50
12.46
9.52
19.4
76.0
162.0
192.0
1.96
1.90
2.00
2.01
2.01
Average 2.0
7
Stoichiometry of cyanidation:
B) Consumption of oxygen
Time
minutes
Ag dissolved
equivalent (x 10
5
)
O
2
consumed
moles (x 10
5
)
[Ag]/[O
2
]
10
20
30
40
120
2.96
7.76
9.36
12.42
36.06
1.45
3.07
4.17
5.40
16.00
2.05
2.50
2.25
2.30
2.25
Average 2.2
Stoichiometry of cyanidation:
C) Formation of hydrogen peroxide
Metal dissolved H
2
O
2
formed
mg
equivalent
(x 10
5
)
mg
moles
(x 10
5
)
Metal
equiv./moles
H
2
O
2
Gold 57.3
47.6
29.0
24.1
5.11
4.02
15.0
11.8
1.93
2.04
Silver 2.96
7.76
9.36
12.42
36.06
1.43
3.09
4.00
5.51
14.76
2.06
2.50
2.24
2.26
2.44
Average 2.3
8
For every 1 equivalent of metal dissolved, 2
moles of cyanide are consumed.
For nearly every 2 equivalents of metal dissolved,
1 mole of oxygen is consumed.
For nearly every 2 equivalents of metal dissolved,
1 mole of H
2
O
2
is produced.
According to this stoichiometry, 1 gram mole of oxygen and 4 gram
moles of NaCN should be present in solution.
At room temperature and at atmospheric pressure, 8.2 mg O
2
are
dissolved in 1 liter of water. This corresponds to 0.27 x 10
3
mol/L.
Accordingly, gold dissolution should occur at a concentration of
NaCN equal to 4 x 0.27 x 10
3
x 49 = 0.05 g/L or 0.005%.
Thus a very dilute sodium cyanide solution would be enough for
dissolving gold.
The fact that oxygen was necessary for dissolution was not readily
recognized because as seen from the above calculations, oxygen in
solution as a result of air solubility is enough to bring about the
reaction.
9
Effect of cyanide concentration
The rate of gold
dissolution increases
linearly with increasing
cyanide concentration
until a maximum is
reached, beyond which a
further increase in
cyanide had no effect.
This was contrary to
common experience since
the rate of dissolution of a
metal, for example, iron in
an acid increased with
increasing acid
concentration.
The explanation of this phenomenon will be
dealt with later.
10
Effect of hydrogen ion concentration
It is essential that the cyanide solution be kept alkaline
during leaching to prevent the formation of HCN which is
a poisonous gas. Hydrogen cyanide may form as a result
of absorption of atmospheric CO
2
:
CO
2
+H
2
O H
2
CO
3
H
2
CO
3
+CN
HCN +HCO
3
+H
2
O HCN +OH
11
The alkalinity of cyanide solutions should,
therefore, be carefully controlled to achieve
high dissolution rates. In practice, the pH
usually ranges from 11 to 12.
12
Solutions kept alkaline by Ca(OH)
2
, when
compared to others at the same pH kept alkaline
with KOH, show a remarkable retarding effect in
the case of lime.
13
The retarding effect is supposed to be due to the
formation of calcium peroxide layer on the surface of the
metal which prevents the reaction with cyanide. Calcium
peroxide was considered to be formed by the reaction of
lime with H
2
O
2
accumulating in solution, according to:
Ca(OH)
2
+2H
2
O
2
CaO
2
+2H
2
O
Lime is one of the reagents commonly used in industry to
adjust the pH of the pulp. Its use must, therefore, be
carefully considered.
Effect of temperature
Increasing the temperature
increases the rate of
dissolution.
On the other hand, the
oxygen content of the
solution decreases with
increasing temperature.
Therefore, there should be
an optimum temperature for
the maximum rate.
This was found to be at
about 85C
14
Effect of agitation
The rate of dissolution increases with
increased agitation,
Effect of foreign ions
Most gold occurs as native metal, nearly all alloyed with various
amounts of silver.
Certain minerals are characteristically associated with gold, and
the most important are pyrite, galena, zinc blend, arsenopyrite,
stibnite, pyrrhotite, and chalcopyrite.
Various selenium minerals and magnetite may also be present.
In Witwatersrand, South Africa, uraninite, and to a lesser extent,
thucholite are associated with the gold ore; uranium is recovered
as a by-product of gold milling.
Carbonaceous matter is associated with some gold ores. The most
common gangue minerals are quartz, feldspar, micas, garnet, and
calcite.
Although the gangue minerals are insoluble in cyanide solution,
some metallic minerals are soluble to some extent.
Carbonaceous matter in gold ore is a source of trouble, because it
adsorbs gold cyanide complex.
15
With the exception of a few ions such as Na
+
, K
+
, Cl
,
NO
3
-
and SO
4
2-
which have no effect on the rate of
dissolution of gold and silver in cyanide solution, ions
may have an accelerating or a retarding effect.
Lead(II) ions may have either an accelerating or a
retarding effect, depending on their concentration in
solution.
The study of the effect of these foreign ions on
cyanidation is complicated because the dissolution
process is composed of two simultaneous reactions: The
oxidation reaction involving the formation of the auro- or
the argento-cyanide ion and the reduction of oxygen as
mentioned above.
Which of these reactions is affected by the foreign
ion is usually difficult to say, and many
contradictory statements are found in the
literature.
Data available were mainly obtained by studying
the effect of foreign ion in the gold leaf test.
16
An approach to this problem is to study the effect
of the foreign ion on the cathodic and the anodic
reactions separately. This can be achieved by
studying the change in potential-current density
characteristics of the gold (or silver) electrode in
two separate experiments:
Gold electrode +[Au(CN)
2
]
+CN
+foreign ion,
oxygen being excluded from the system.
Gold electrode +O
2
+H
2
O +foreign ion, in the
absence of cyanide ion.
In the first experiment, the effect of the foreign ion on the
reduction of oxygen on the gold surface can be studied,
and in the second experiment, the effect of the same ion
on the anodic reaction of gold dissolution in cyanide.
The results of such tests should be interpreted with care,
however, as the application of external emf to cause
dissolution does not correspond to actual cyanidation
practice.
Thus, for example, under these conditions oxygen is
reduced to OH
and not to H
2
O
2
.
Another approach involves the use of radioactive
indicators of the ions being studied
17
Accelerating effect
It has been reported that small amounts of lead, bismuth, thallium, and
mercuric salts accelerate the dissolution. This was confirmed later by
many researchers.
From calculations of electrode potentials in cyanide solutions, it was
concluded that gold metal can actually displace the ions of onlythese
four metals.
It was, therefore, suggested that the rapid dissolution of gold in the
presence of these ions might be due to alteration in the surface
character of gold by alloying with the displaced metals.
Early researchers detected the presence of lead on the surface of gold
when the cyanide solution contained Pb
2+
ions, but did not identify its
nature.
It was recently confirmed
by electron microscopic
studies that lead alloys
with gold on the surface.
The alloy then dissolves
rapidly, hence lead acts as
a catalyst.
18
The presence of metallic cations such as Fe
2+
, Cu
2+
, Zn
2+
, Ni
2+
,
Mn
2+
, Ca
2+
, and Ba
2+
(the latter two only at high alkalinity) has a
retarding effect.
Lead(II) plays a unique role in cyanidation, and there has been
much confusion regarding its effect on the rate of dissolution of
gold.
Besides the accelerating action already described, some reports
describe a retarding effect.
It can be concluded from those studies that when Pb
2+
is present in
very small amounts as compared to the CN
ion, an accelerating
effect is observed, whereas when the [Pb
2+
]/[CN
] ratio exceeds a
certain value there is a retarding effect.
It is also known that the sulfide ion and
certain flotation agents such as xanthate ion,
which is sometimes used to concentrate the
sulfides with which gold is associated have a
retarding effect on the rate.
19
Retarding effect may be due to one or more
of the following reasons:
Consumption of oxygen from solution
Consumption of free cyanide from solution
Film formation on the surface of the metal
Consumption of oxygen from solution
Because oxygen is necessary for gold dissolution,
any side reactions in which the cyanide solution is
deprived of its oxygen content will lead to a
decrease in the rate.
Pyrrhotite accompanying gold in some ores
decomposes in alkaline medium forming ferrous
hydroxide and sulfide ion:
FeS+2OH
Fe(OH)
2
+S
2
20
In presence of oxygen, ferrous hydroxide is easily
oxidized to ferric hydroxide:
2Fe(OH)
2
+
1
/
2
O
2
+H
2
O 2Fe(OH)
3
while sulfide ion is partly oxidized to thiosulfate
and polysulfide:
2S
2
+2O
2
+H
2
O S
2
O
3
2
+2OH
S
2
+H
2
O HS
+OH
2HS
+
1
/
2
O
2
S
2
2
+H
2
O
thus contributing to the depletion of oxygen from
solution.
Consumption of free cyanide from solution
Formation of complex cyanides: Some copper, zinc, and iron
minerals that may be associated with gold ore dissolve in cyanide
solution and therefore deplete the solution of its cyanide content,
e.g.:
ZnS + 4CN
[Zn(CN)
4
]
2
+ S
2
Formation of thiocyanate: Sulfide ion liberated, when the ore
contains sulfide minerals, reacts with cyanide and oxygen to form
thiocyanate ion, which has no action on gold:
S
2
+ CN
+
1
/
2
O
2
+ H
2
O CNS
+ 2OH
Fe(OH)
2
+S
2
2Fe(OH)
2
+
1
/
2
O
2
+H
2
O 2Fe(OH)
3
S
2
+2O
2
SO
4
2
SO
4
2
+Ca
2+
CaSO
4
The sulfide-free pulp is then subjected to
cyanidation.
Rec ent advanc es
24
Thiourea process
The solubilizingaction of gold and silver in thioureamay
be represented by the oxidationreduction couple as
follows:
Au Au
+
+e
Au
+
+2(NH
2
)
2
CS
[(H
2
N)
2
CSAuSC(NH
2
)
2
]
+
Fe
3+
+e
Fe
2+
This takes place in acid medium, is faster than
cyanidation, and less toxic.
However, thioureaundergoes appreciable decomposition
during leaching
Heap leaching
The increased price of gold in the 1970s made
possible the leaching of old tailings containing as
little as 1 ppm gold thanks to the newly developed
heap leaching technology that was developed for
the leaching of low grade copper and uranium ores.
To improve the percolation of the leach solution in
the bed, the fine tailings were sometimes
agglomerated by slurrying with water and a small
amount of cement which was allowed to set.
The heaps were then constructed from the hard
agglomerates and leached with the alkaline cyanide
solution.
25
Treatment of refractory ores
A problem in gold metallurgy was the treatment of gold locked up
in pyrite or arsenopyrite crystals and therefore unresponsive to
cyanidation.
Roasting followed by leaching is an expensive and polluting
proposition.
A hydrometallurgical approach proved to be a successful solution
for this type of ores.
Barrick Goldstrike now treats a pyrite orewater slurry in
autoclaves at high temperature and oxygen pressure. Horizontal
autoclaves are used, each being 30 m long and 5 m in diameter,
operating at 160180 C and 2000 kPa, with a retention time of 20
minutes (Figures and ). The autoclaves are made of carbon steel 8
cm thick, lined with as 6 mm lead membrane and two layers of
acid-resisting brick 22.5 cm total thickness.
After this treatment, the ore is then suitable for cyanidation.
26
Pressure leaching operation for treating refractory
gold ores prior to cyanidation at Elko, Nevada
Inside Barrick
Goldstrike plant
27
Start up Plant location Owner Feed Medium Capacity, t/d
Number
of
autoclaves
1985 McLaughlin,
USA
Homestake,
USA
ore acid 2700 3
1986 San Bento,
Brazil
Genmin,
South Africa
concentrate acid 240 2
1988 Mercur,
Utah, USA
American Barrick,
Canada
ore alkaline 680 1
1989 Getchell, USA First Miss Gold ore acid 2730 3
1990 Goldstrike,
Nevada, USA
American Barrick,
Canada
ore acid 1360 1
1991 Goldstrike,
Nevada, USA
American Barrick,
Canada
ore acid 5450 3
1991 Pargera, Papua
New Guinea
Placer Dome,
Canada
concentrate acid 1350 3
1991 Campbell,
Canada
Placer Dome,
Canada
concentrate acid 70 1
1992 Con, Lihir Nerco Minerals concentrate 90 1
1993 Goldstrike, USA American Barrick,
Canada
ore acid 11580 6
1994 Pargera,
PapuaNew Guinea
Placer Dome,
Canada
concentrate acid 2700 6
Under
study
Lihir, PapuaNew
Guinea
Gold ores containing carbonaceous
material
Gold ores containing carbonaceous material are also known as
refractory ores and are difficult to treat, not only because part of
the gold is tied up with the organic matter but also because
dissolved gold is adsorbed on the carbon present in the ore and
therefore reports in the taillings.
This problem was solved by aqueous oxidation using chlorine.
Some of the gold may be solubilized by the chlorine water but the
major function of the controlled chlorination is to oxidize organic
matter before cyanidation.
A plant at Carlin, Nevada, uses this technology.
Another solution to this problem was found by using the carbon-in-
leach process
28
Cyanidation under pressure
Cyanidation under high oxygen pressure has been used
commercially at the Consolidated Murchison Mine near Gravellote
in South Africa.
The process has been developed by Lurgi in Germany using tube
autoclaves 1.5 km long and 5 cm inner diameter.
Leaching is conducted at ambient temperature but at about 5 MPa
oxygen pressure.
As a result, residence time is only 15 minutes at 85% recovery. It
should be noted that at high oxygen pressure, a high cyanide
concentration must be used to achieve high reaction rates.
In practice the leach solution is 0.2% to 0.5% NaCN. Although
cyanide solutions are susceptible to oxidation, the short residence
time renders this drawback negligible.
MECHANISM OF CYANIDATION
Cyanidation reaction is a heterogeneous process
involving a solid [the ore], a liquid [the aqueous
cyanide solution], and a gas [air or oxygen].
A homogeneous process takes place in one phase
only; it can be in a gas phase for example, the
reaction of hydrogen and chlorine to form HCl, or a
liquid phase for example, the neutralization of an
acid by a base.
Heterogeneous reactions take place between more
than one phase; the surface separating the phases
is called interface at which the reacting species have
to be transferred.
29
The interface
The interface is the boundary between two
phases.
For example, in a solidgas reaction the
interface is the outside surface of the solid in
contact with the gas.
For two immiscible liquids, the interface is the
surface of contact between the two liquids.
For a solid-liquid reaction the interface is the
surface of the solid.
Lattice defects, non-stoichiometry, and
impurities at the interface influence the rates
of chemical reactions.
When a product layer is formed on the
reacting solid the kinetics of these reactions
will evidentally be governed by the character
of this coating whether it is porous or
nonporous.
30
Only two phases are actually taking part in any
heterogeneous process, although more may be
present in the reaction mixture.
The reason is that the overall rate of reaction is
determined by the rate of a single step the rate-
determining step, which is slower than all others.
For example, the dissolution of gold (solid) in
sodium cyanide solution (liquid) in presence of
oxygen (gas), the process is reduced to a solid
liquid reaction since oxygen can be transferred from
the gas phase to the liquid phase at a faster rate
than the other reactions taking place.
The boundary layer
A solid in contact with a liquid is covered by a stagnant
film of liquid about 0.03 mm in thickness called the
Nernst boundary layer.
The existence of this layer is manifested when a liquid is
flowing in a pipe in a streamline flow, the velocity of the
liquid will be maximum at the center and gradually
decreases to zero at the inside walls.
This concept was first applied to explain the dissolution
of solids and was later extended to other heterogeneous
reactions such as solidgas and liquidliquidreactions.
31
When a solid C is agitated in water and the
solution is analyzed at intervals, it will be found
that the rate of increase of the solute
concentration follows the equation
where [C] is the concentration of the solute at time t, [C]
s
is its solubility in
water at the experimental temperature, i.e., its concentration at saturation,
and k is the velocity constant.
C | | d
t d
----------- k | |
s
C | | ( ) =
32
C | | d
| |
s
C | |
-------------------------
0
C | |
}
k t d
t
}
=
C | |
s
C | | ( ) ln d
0
C | |
}
k t d
t
}
=
2.303
C | |
s
C | |
s
C | |
-------------------------
log kt =
The plot of log [C]
s
/([C]
s
[C]) against t gives a
straight line.
It was therefore suggested that a saturated layer is
rapidly formed at the interface and that the
observed velocity is the rate at which the solvate
molecules diffuse through this layer into the bulk
of the solution.
33
Diffusion
Diffusion is the tendency of any substance to
spread uniformly throughout the space available
to it.
It is a result of molecular movement; no other
outside force is influencing the mixing action.
It is exhibited by gases, liquids, and solids, but it
is most rapid in gases, and most slow in solids.
Diffusion in gases, liquids, and solids in governed
by Fickslaw.
Ficks law
t d
dn
DA
X d
dC
=
A
dx
C
1
2 1
>
34
Where dn is the quantity of a dissolved substance which
diffuses in time dt through the cross-sectional area A,
from the direction of high concentration to that of low
concentration, and is proportional to the concentration
gradient in the direction of diffusion dC/dX and the cross
section A.
D is the diffusion coefficient of the substance and
defines the quantity (grams or moles) diffusing in unit
time through a cross section of 1 cm
2
, when the
concentration gradient is unity.
The concentration must be expressed in the same units.
The diffusion coefficient is usually expressed in cm
2
sec
1
.
Effect of temperature on the
diffusion
The effect of temperature on
the diffusion in aqueous
solution follows the Stokes
Einstein equation.
Where R is the gas
constant, N is Avogadros
number, the viscosity of
the medium, and r is the
radius of the diffusing
molecule (supposedly in
the form of a sphere).
D
RT
6trqN
----------------- =
35
Applying Ficks law of diffusion to
cyanidation process
t d
dn
DA
o
---------
C | |
s
C | | ( ) =
Where n =the number of
species diffusing in unit
time, D=the diffusion
coefficient, A =surface
area of the solid, and o =
the thickness of the
saturated layer adhering to
the surface of the solid,
i.e., the boundary layer.
Since C | |
n
V
--- =
where V is the volume of solution, the above equation becomes:
C | | d
t d
-----------
D
o
-----
A
V
---
| |
s
C | | ( ) =
36
Thus, the rate constant k can be identified by DA/dV. This
equation explained the following observations:
- The rate of dissolution of a solid in water increased with
increased agitation because the thickness of the boundary
layer decreased.
- The rate of dissolution was not influenced by increased
temperature; an activation energy < 5 kcal/mole was
usually observed. This is in agreement with a physical
process such as diffusion.
Types of het er ogeneous r eac t i ons
It was first thought that all dissolution processes
were controlled by diffusion.
But, when many processes were studied and it was
found that in some cases the rates were
independent of stirring and the activation energy
was higher than 5 kcal/mole, it was concluded that,
only physical processes are diffusion-controlled, but
chemical and electrochemical reactions may be
diffusion-controlled, chemically controlled, or
intermediate-controlled reactions.
37
Physical processes
The dissolution of an ionic solid such as NaCl
in water is a typical example.
A crystal of the salt immersed in a certain
volume of water will be immediately covered
by a thin layer of a saturated solution of NaCl.
The ions will then diffuse spontaneously in
water following Ficks law until the whole
volume of water becomes a saturated
solution.
Chemical processes
Consider an ionic or a
covalent solid in form of a
plate of surface area A in
contact with an aqueous
solution containing a
reagent R that reacts with
the species C dissolving
from the solid.
At the interface, the
concentration of the
solute will be that of a
saturated solution, [C]
s
,
and in the bulk of solution
will equal [C].
38
Three cases may be considered:
When the rate of reaction of the reagent with the dissolving
species in the bulk of the solution is very fast, then the
concentration of C will equal zero and the process will be
controlled by the rate of diffusion of C through the boundary
layer.
When the rate of reaction of the reagent with the dissolving species
in the bulk of the solution is very slow, then the diffusion does not
play any role, and there will be accumulation of C in solution, i.e.,
[C] ~ [C]
s
. The rate of reaction will, therefore, depend on the
concentration of the reagent R since [C]
s
is constant, i.e., the
process is chemically controlled.
When the rate of reaction of the reagent with the dissolving
species in the bulk of the solution equals that of the rate of
diffusion, then the process is known as intermediate
control.
Electrochemical processes
This is the case of a metal or a semiconducting
solid which reacts through an oxidationreduction
process, i.e., transfer of electrons.
The reagent in solution of concentration [D]
diffuses through the boundary layer to pick up
electrons from the interface.
The symbol D stands for depolarizer, i.e., an
oxidant.
39
The liberated metal ion would hydrolyze forming
insoluble compounds that would block the anodic
zone and the reaction would stop unless a
complexingagent is present.
If [D] =the concentration of the depolarizer, [C]
=the concentration of the complexingagent, A
1
=
the surface area of the cathodiczone, A
2
=the
surface area of the anodic zone, k
1
and k
2
are the
velocity constants at the cathodicand the anodic
zones, respectively, then:
40
V
1
=k
1
A
1
[D] and V
2
=k
2
A
2
[C]
where V
1
and V
2
are the velocity of the cathodic
and the anodic reactions, respectively.
At the steady state, the rate of the cathodic
reaction equals that of the anodic reaction, i.e.:
k
1
A
1
[D] =k
2
A
2
[C]
A
1
2
------
k
2
C | |
1
D | |
-------------- - =
41
A
1
1 2
+
------------------
k
2
C | |
1
D | |
2
C | | +
------------------------------------ =
A
2
1 2
+
------------------
k
1
D | |
1
D | |
2
C | | +
----------------------------------- - =
Therefore:
A
1
k
2
C | |
1
D | |
2
C | | +
------------------------------------
=
A
2
k
1
D | |
1
D | |
2
C | | +
------------------------------------
=
42
where A is the total surface area of the solid in
contact with the solution:
A =A
1
+A
2
Substituting the value of A
1
(or A
2
) in any of the
rate equations, gives the following:
Rate of dissolution
k
1 2
A D | | C | |
1
D | |
2
C | | +
------------------------------------ =
[D] = the concentration of the depolarizer
[C] = the concentration of the complexing agent A
1
= the
surface area of the cathodic zone
A
2
= the surface area of the anodic zone
k
1
and k
2
are the velocity constants at the cathodic and the
anodic zones, respectively, then:
V
1
= k
1
A
1
[D] and V
2
= k
2
A
2
[C]
where V
1
and V
2
are the velocity of the cathodic and the
anodic reactions, respectively.
At the steady state, the rate of the cathodic reaction equals
that of the anodic reaction, i.e.:
43
k
1
A
1
[D] =
2 2
[C]
A
1
2
------
k
2
C | |
1
D | |
--------------- =
A
1
1 2
+
------------------
k
2
C | |
1
D | |
2
C | | +
----------------------------------- - =
2
1 2
+
------------------
1
D | |
1
D | |
2
C | | +
----------------------------------- - =
Therefore:
A
1
k
2
C | |
1
D | |
2
C | | +
------------------------------------
=
2
1
D | |
1
D | |
2
C | | +
------------------------------------
=
where A is the total surface area of the solid in contact with
the solution:
A = A
1
+ A
2
Substituting the value of A
1
(or A
2
) in any of the rate
equations, gives the following:
Rate of dissolution
k
1 2
A D | | C | |
1
D | |
2
C | | +
------------------------------------ =
44
This equation has the following characteristics:
At low concentration of C, the second term in the denominator may be
neglected in comparison with the first, and the rate equation simplifies to:
Rate = k
2
A[C]
i.e., the rate of dissolution in this case is only a function of the hydrogen ion
or the complexing agent concentration.
At high concentration of C, the first term in the denominator may be
neglected in comparison with the second, and the velocity equation simplifies
to
Rate = k
1
A[D]
i.e., the rate of dissolution under these conditions depends only on the
concentration of the depolarizer.
When the first and second terms in the denominator are of equal magnitude,
i.e., when
k
1
[D] = k
2
[C]
then the rate of dissolution reaches its limiting value, i.e., when the rate curve
changes its direction. This change takes place at a certain ratio of [C]/[D], as
can be deduced from the equation:
C | |
D | |
---------
k
1
2
----- Constant = =
The process was found to be strongly dependent on the speed of agitation,
and the activation energy to be < 5 kcal/mole which are the characteristics
of a diffusion-controlled process.
Cathodic reaction: O
2
+ 2H
2
O + 2e
OH
+ H
2
O
2
Anodic reaction: Au Au
+
+ e
Au
+
+ 2CN
[Au(CN)
2
]
Overall reaction:
2Au + 4CN
+ O
2
+ 2H
2
O 2[Au(CN)
2
]
+ 2OH
+ H
2
O
2
45
According to Ficks law,
O
2
| | d
t d
--------------
D
O
2
o
----------
A
1
O
2
| | O
2
| |
i
( ) =
CN
| | d
t d
-------------------
D
CN
o
-------------
A
2
CN
| | CN
| |
i
( ) =
Since the process is diffusion-controlled,
[O
2
]
i
= 0 and [CN
]
i
= 0
O
2
| | d
t d
--------------
D
O
2
o
----------
A
1
O
2
| | =
CN
| | d
t d
-------------------
D
CN
o
-------------
A
2
CN
| | =
46
Since the amount of metal dissolved is twice that of oxygen consumed
and half that of cyanide consumed as can be seen from the overall
equation, therefore:
Rate of dissolution 2
O
2
| | d
t d
--------------
D
O
2
o
----------
A
1
O
2
| | = =
1
2
---
CN
| | d
t d
-------------------
=
---
D
CN
o
-------------
A
2
CN
| | =
It follows from these equations that, at the steady state:
2
D
O
2
o
----------A
1
O
2
| |
1
2
---
D
CN
o
-------------
2
CN
| | =
But, since A, the total surface area of metal in
contact with the aqueous phase = A
1
+ A
2
, therefore:
Rate
2AD
CN
D
O
2
CN
| | O
2
| |
o D
CN
CN
| | 4D
O
2
O
2
| | + ( )
----------------------------------------------------------------------- =
47
At low cyanide concentration, the first term in
the denominator may be neglected in
comparison with the second, so that the
equation simplifies to:
Rate
1
2
-- -
AD
CN
o
-----------------
CN
| | =
= k
1
[CN
]
At high cyanide concentration, the second
term in the denominator may be neglected in
comparison with the first, and the equation
simplifies to:
Rate 2
AD
O
2
o
--------------
O
2
| | =
= k
2
[O
2
]
48
When D
CN
CN
| | 4D
O
2
O
2
| | =
CN
| |
O
2
| |
---------------- 4
D
O
2
D
CN
-------------
=
the rate of dissolution reaches its limiting value.
49
D
O
2
= 2.76 10
5
cm
2
sec
1
and D
KCN
= 1.83 10
5
cm
2
sec
1
CN
| |
O
2
| |
---------------- 6 =
Experimental data showed that the rate of gold
dissolution was 3 mgcm
2
hr
1
in a 0.25% NaCN
solution at atmospheric pressure with air agitation.
On using unified units: rate = 4.22 10
9
gequivalentcm
2
sec
1
, [NaCN] = 51 10
6
MmL
1
, = 0.21 atm = 0.27 10
6
MmL
1
, then:
50
4.22 10
9
2 1 1.83
5
10 2.76
5
10 51
6
10 ( ) 0.27
6
10 ( )
o 1.83
5
10 51
6
10 ( ) 4 2.76
5
10 0.27
6
10 ( ) + | |
---------------------------------------------------------------------------------------------------------------------------------- =
139
22
10
o 93
11
10 3
11
10 + ( )
-------------------------------------------------------- =
o = 3.4 10
3
cm
THANKS
1
EXTRACTIVE METALLURGY OF EXTRACTIVE METALLURGY OF GOLD GOLD
5 5. Enrichment in solution . Enrichment in solution
Fat hi Habashi Fat hi Habashi
Laval University, Quebec City, Canada Laval University, Quebec City, Canada
Fathi.Habashi@arul.ulaval.ca Fathi.Habashi@arul.ulaval.ca
Concentration Concentration - - Purification Purification
Adsorption on activated charcoal
Ion exchange
Solvent extraction
2
Adsorption
on activated
charcoal
Ion exchange Solvent extraction
Maximum
efficiency
dilute
solution
dilute solution concentrated
solution
Speed slow slow rapid
Capacity low high high
Clarity of
solution
clear or
turbid
clear or turbid clear
Method of
operation
batch or
semi-
continuous
batch,
semi-
continuous, or
continuous
continuous
Cost low high moderate
Mechanism physical physico-
chemical
chemical
Adsorption & Ion Exchange
Adsorption & Ion Exchange
1.
Sorption
Feed or
influent
Effluent
to waste
Washing
Water
Loosely
sorbed
effluent
to waste
2.
Elution
Eluent
Eluate
for metal
recovery
Washing
Water
To waste
3
Solvent Extraction
Solvent Extraction
Leach
solution
Barren
solution
(raffinate)
Organic phase
(loaded)
Organic phase
recycle
(unloaded)
Strip
solution
Strip
solution
recycle
Pure metal salt for
reduction to metal
Precipiteting
agent
Extraction Stripping Recovery
4
Varieties of Carbon
Varieties of Carbon
Carbon black
Prepared by the incomplete combustion of gaseous or liquid
carbonaceous material, e.g., natural gas, acetylene, oils, resins, tar,
etc., in a limited supply of air. It is nonporous fine particles of carbon.
Example: lamp black and acetylene black. Used as pigments, in the
rubber industry, and in ink manufacture.
Charcoals
Prepared by heating of solid carbonaceous material such as coal,
wood, nut shells, sugar, and synthetic resins at about 600 C in the
absence of air, to volatilize the component elements other than carbon
a process known as carbonization . Such charcoals have low
porosity
Activated charcoal
Prepared by heating charcoal at 400800C for a limited time with air,
chlorine, or steam. A highly porous material is produced. Used as an
adsorbent in the chemical and the metallurgical industry, usually in
the form of pellets about 2 mm in diameter.
5
Charcoal vs.
Graphite
Activated Charcoal Activated Charcoal
Surface Oxides Surface Oxides
OH
C
=
O
H
O O
O
O
OH
OH
C
C
O
O
=
O
C
=
C
O
O
Carboxylic
acid
Phenolic
hydroxyl
Quinone
carbonyl
Carboxylic
anhydride
Cyclic
peroxide
Fluorescein
lactone
Normal
lactone
6
Activated Charcoal Activated Charcoal
Effect of Oxygen on Adsorption Effect of Oxygen on Adsorption
100
80
60
40
20
0
20 60 100
A
c
i
d
a
d
s
o
r
p
t
i
o
n
,
m
e
q
u
i
v
.
/
g
Oxygen pressure, mm Hg
ADSORPTION
ADSORPTION
Mechanism
Mechanism
Surface
Bulk of solid
7
Adsorption Isotherm 1
Adsorption Isotherm 1
Emperical Emperical
Freundlich FreundlichIsotherm Isotherm
Gases Gases w =kp
1/n
Aq. Solutions Aq. Solutions w =kC
1/n
Adsorption Isotherm 2
Theoretical: Langmuir
Theoretical: Langmuir
kp(1 ) = k
8
Adsorption of Gold & Silver
Adsorption of Gold & Silver
from cyanide solution
from cyanide solution
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0 1 2 3
Log concentrati on i n sol uti on
L
o
g
c
o
n
c
e
n
t
r
a
t
i
o
n
i
n
c
h
a
r
c
o
a
l
[Au(CN)2]
[Ag(CN)2]
CN
Adsorption
Adsorption
Effect of Temperature
Effect of Temperature
400
300
200
100
0
2.5 5.0 7.5 10.0 12.5 0
S
i
l
v
e
r
o
n
c
h
a
r
c
o
a
l
m
i
c
r
o
m
o
l
e
s
A
g
/
g
c
h
a
r
c
o
a
l
Silver in solution, millimolesAg/L
25 C
40 C
54 C
63.5 C
73.5 C
9
Adsorption
Adsorption
effect of organic solvents
effect of organic solvents
100
90
80
70
60
50
40
30
20
10
0 5 10 15 20
Number of bed vol umes
of stri p sol uti on
G
o
l
d
d
e
s
o
r
p
t
i
o
n
%
Wi th 20%
ethanol
Wi thout
ethanol
De
De
-
-
sorption
sorption
Effect of Temperature
Effect of Temperature
100
90
80
70
60
50
40
30
30 40 50 60 70 80 90 100
G
o
l
d
d
e
s
o
r
p
t
i
o
n
%
Temperature, C
10
Engineering Aspects 1 Engineering Aspects 1
Sorption of the gold cyanide complex on charcoal.
Washing with water to remove the entrained solution.
Desorption, usually with a solution of 0.2% NaCN
and 1% NaOHat 90C.
Acid washing to remove CaCO
3
precipitate.
Washing the depleted charcoal with water to remove
the entrained solution.
Dewatering, activation by heating for 30 minutes at
700C in absence of air, then quenching and
recycling.
Engineering Aspects 2 Engineering Aspects 2
Two factors contribute to the choice of the
adsorption process:
Filtration properties of the pulp
Presence of organic matter in the ore
11
Engineering Aspects 3 Engineering Aspects 3
Column process
Clear solutions
Carbon-in-pulp process
Ores containing finely divided clay particles which are difficult to filter. In
this process, the cyanide leaching pulp is agitated in tanks with the charcoal
pellets . When adsorption is complete, the pulp is screened to separate the
gold-laden pellets for washing and de-sorption. The process has the
advantage of eliminating filtration.
Carbon-in-leach process
Ores containing organic matter
Adsorption on Charcoal Adsorption on Charcoal
SUMMARY
SUMMARY
Activated charcoal is hydrophilic because of the
organic surface complexes formed during activation.
It has a large surface area and a high porosity
Adsorption of gold or silver cyanide complexes is a
physical process
Oxygen is necessary for adsorption processes
Adsorption decreases when the solution contains an
organic solvent of lower polarity than water since
under these conditions the electrostatic forces of
attraction decrease
Adsorption decreases with increased temperature
12
Ion Exchange
Ion Exchange
Ion Exchange 2
Ion Exchange 2
+
+
+
+
+
+
+ +
+
+
+
+
+
+
+
+
+
+
+
Matri x
Hol es
13
Ionogenic
Ionogenic
Groups
Groups
A matrix carries a positive or a negative
electric charge
This is compensated by ions of opposite
sign, called counter-ions
Ions of the same sign as that on the
framework are called co-ions
The counter-ions are free to move within
the framework and can be replaced by
other ions of the same sign, while the
fixed ions are not mobile
Ion Exchange Equations
14
Ion Exchange Equipment
Ion Exchange Equipment
Columns. Columns. Clear solutions Clear solutions
Resin Resin- -in in Pulp. Pulp. Slurry Slurry
Continuous system. Continuous system. Clear solutions Clear solutions
Resin
Resin
-
-
in
in
-
-
Pulp
Pulp
Top of
stroke
Bottom of
stroke
Reciprocating rod
Stainless steel
angle frame
Stainless steel screen on
four sides and bottom
Binder strip
bolted to frame
15
Continuous Ion Exchange System
Mixer Settlers
Leach
Strip
U
n
l
o
a
d
e
d
O
r
g
a
n
i
c
Rafinate
EXTRACTION
STRIPPING
Strip
solution
solution
to metal
recovery
(recycle to
leaching)
solution
Leach
Wash
U
n
l
o
a
d
e
d
O
r
g
a
n
i
c
L
o
a
d
e
d
EXTRACTION
Wash
solution
Strip solution
STRIPPING
to metal recovery
solution
solution
Rafinate
(recycle to
leaching)
Strip
solution
Aqueous
Organic
Organic
Aqueous
Mixer Settler
16
Columns
Interface
Interface
Solvent
i nl et
Sol vent
i nl et
Aqueous
i nl et
Aqueous
i nl et
Solvent
outl et
Solvent
outl et
Aqueous
outl et
Aqueous
outl et
Piston
pl ates
Perforated
Loaded solvent
Raffinate
Aqueous
feed
Solvent
feed
THANKS
1
EXTRACTIVE METALLURGY OF EXTRACTIVE METALLURGY OF GOLD GOLD
6 6. Recovery from solution . Recovery from solution
Fat hi Habashi Fat hi Habashi
Laval University, Quebec City, Canada Laval University, Quebec City, Canada
Fathi.Habashi@arul.ulaval.ca Fathi.Habashi@arul.ulaval.ca
2
Precipitation by zinc
This method is known by the name of its
inventors Merrill-Crowe.
The clear leach solution is first de-aerated, then
zinc dust added to precipitate gold and silver.
De-aeration is essential to prevent the re-
dissolution of gold.
Precipitation by metallic zinc is an oxidation -
reduction process that takes place as a result of
displacing the equilibrium of the complex ion.
2[Au(CN)
2
]
+ Zn 2Au + [Zn(CN)
4
]
2
[Au(CN)
2
]
Au
+
+2CN
Zn Zn
2+
+2e
-
Au
+
+e
-
Au
Zn
2+
+4CN
[Zn(CN)
4
]
2
3
Analysis of typical precipitates from a Merrill-Crowe process
S. Africa,
%
USA, %
Au 30-40 14.4
Ag 3-6 0.35
Cu 1-4 0.9
Zn 5-25 9.4
Pb 5-15 2.1
Fe ---- -----
S ---- 4.6
SiO
2
---- 25.7
Directly smelted with fluxes to produce
bullion. This usually applies to high grade
ores containing 10-25 g/t gold
Acid leaching to remove excess zinc, calcinationto
oxidize other impurities, then smelting with fluxes
to produce bullion. This usually applies to low
grade ores containing ~5 g/t gold
Acid leaching followed by retorting to remove
mercury if present, then smelting with fluxes to
produce bullion
4
Acid leaching must be conducted under a
well ventilated hood since toxic and
explosive gases such as hydrogen sulfide,
hydrogen, and arsine are evolved.
Calcination of the solids is usually
conducted on stainless steel trays
mounted in an electric furnace
5
Each tray contains approximately 60 kg of moist
gold slime and the furnace can accommodate
six to twelve trays.
Calcination takes place at 600-700
o
C for a
period of about 16 hours.
After calcinations, the gold powder is mixed with
a flux, mainly composed of borax and silica.
Smelting is essential to produce good grade
bullion that can be accurately sampled and
assayed for its gold and silver content, and can
be easily transported to the refinery.
Smelting is conducted in a three electrode submerged
arc tilting furnace. The gold powder and flux is
added portion wise, 100 kg at a time.
The smelting cycle occupies about three hours,
comprising one hour for charging the furnace, one
and half hours for fusion, and half an hour for slag
removal and pouring.
Smelting temperatures ranges from 1200 to 1400
o
C.
When fusion is complete, the three carbon electrodes
are withdrawn and the furnace tilted from the vertical
towards the horizontal position to pour the molten
contents through the discharge spout.
6
7
The gold bullion is poured into standard
moulds which are designed to contain bars of
31 kg. Once the gold has solidified, the bars
are quenched in water and cleaned by hand
scrubbing.
The bars are then sampled by hand-drilling.
The arc furnace is normally operated with
electrodes set at 600 amperes and the life of the
carbon electrodes ranges from 6 to 10 fusions.
The average life of the furnace liner is 35 fusions
but this figure can be extended if repairs are
made between fusions.
A ventilation hood is installed above the furnace
and all fumes and dust emanating from the
furnace are withdrawn though a fan and passed
into a filter.
All fine particles trapped in the filter are collected
and returned to the ensuing furnace charge.
8
The resulting slag from smelting is usually returned to
the mill circuit for recovering any gold it may contain.
Fire bricks and furnace liners, when replaced, are
crushed, passed over a shaking table to recover gold
beads, and then also sent to the mill.
Floor sweepings, dust from the smelt-house walls and
the deposit in the ventilation filters are handled in the
same way.
In general, all material leaving the smelt-house is
returned to the milling circuit for gold recovery and final
disposal.
Processing after enrichment by activated charcoal
The enriched solution obtained after
elution of the charcoal may then be treated
by two methods depending on the
concentration of gold in solution:
Electrowinning
Precipitation by zinc
9
Electrowinning
This method is applied when the solution
is relatively rich and may be conducted in
the following ways:
Deposition on steel wool cathodes
followed by smelting to prepare a bullion.
Deposition on stainless steel wool
cathodes followed by reversing the polarity
and electroplating the gold, then melting to
produce a bullion.
10
11
Precipitation by zinc
This method applies for dilute solutions
and the procedure followed is the same as
the one previously mentioned.
Enrichment by ion exchange followed by
electrowinning
This method is used only in one plant at
Muruntau Mine in Uzbekistan.
The process is rather complex and costly
because of high consumption of reagents.
If weak base resin is used, the pH of the
solution must be adjusted to an
undesirably low levels, and if strong base
resin is used it is difficult to strip the
loaded resin.
12
Enrichment by solvent extraction followed by
precipitatinon
Extraction of gold cyanide complex by
organic solvents such as alkyl phosphorus
esters and amines.
No industrial development followed.
1
EXTRACTIVE METALLURGY OF EXTRACTIVE METALLURGY OF GOLD GOLD
6 6. Recovery from solution . Recovery from solution
Fat hi Habashi Fat hi Habashi
Laval University, Quebec City, Canada Laval University, Quebec City, Canada
Fathi.Habashi@arul.ulaval.ca Fathi.Habashi@arul.ulaval.ca
Refining Refining is is a a necessary necessary step step in in treating treating a a metal metal
to to decrease decrease its its impurities impurities so so that that it it can can be be used used
for a for a variety variety of of purposes purposes. .
Physical Physical and and electrochemical electrochemical properties properties of a of a
metal metal are are greatly greatly influenced influenced by the by the level level of of
impurities impurities. . Thus Thus ductility ductility, , electrical electrical
conductivity conductivity, and , and other other properties properties improve improve
remarkably remarkably with with increased increased purity purity. .
Refining Refining is is, , therefore therefore, an important , an important
metallurgical metallurgical operation operation. .
2
New techniques have to New techniques have to be be developed developed for for
producing producing pure pure metals metals and new and new methods methods
of of analysis analysis have been have been devised devised for for quality quality
control. control.
Raw Raw gold gold ingots ingots produced produced at at the mine site the mine site
or or scrap scrap gold are gold are shipped shipped to to refiners refiners for for
obtaining obtaining pure pure ingots ingots by by pyro pyro- - , hydro , hydro- - , or , or
electrometallurgical electrometallurgical methods methods. .
Silver Silver refining refining is is almost almost always always associated associated
with with a gold a gold refinery refinery. .
Fire Fire assay assay is is still still widely widely used used for gold for gold
determination determination in in raw raw ingots ingots. .
PYROMETALLURGICAL
PYROMETALLURGICAL
REFINING
REFINING
Refining of gold bullion by selective oxidation using Refining of gold bullion by selective oxidation using
chlorine gas is known as the Miller Process after its chlorine gas is known as the Miller Process after its
inventor Francis B. Miller (1828 inventor Francis B. Miller (1828- -1887), and is used at 1887), and is used at
some mints. some mints.
In this process the bullion is melted, then poured into In this process the bullion is melted, then poured into
heated clay crucibles containing borax, which forms a heated clay crucibles containing borax, which forms a
molten layer on the surface of the bullion. molten layer on the surface of the bullion.
The crucibles, about 20 cm in diameter and 30 cm high, The crucibles, about 20 cm in diameter and 30 cm high,
are heated in a furnace. are heated in a furnace.
Each crucible is provided with a slotted cover to allow Each crucible is provided with a slotted cover to allow
inserting or withdrawing of clay pipes through which inserting or withdrawing of clay pipes through which
chlorine is admitted. chlorine is admitted.
As a safeguard against leakage or breakage, each As a safeguard against leakage or breakage, each
crucible is placed inside a graphite crucible. crucible is placed inside a graphite crucible.
3
The base metals are attacked first and volatilize
as chlorides.
They are collected in a flue dust recovery system.
After the base metals have been practically
eliminated, silver is attacked next and AgCl (m.p.
455C) floats on the surface of the gold beneath
the borax layer.
It is skimmed off and collected for silver
recovery.
Chlorination is complete and the gold is ready for
casting when a clay rod held in the fumes forms
a brownish stain indicating the formation of gold
chloride.
4
HYDROMETALLURGICAL REFINING HYDROMETALLURGICAL REFINING
Small scale refining of gold, e.g., in mints, is
done by selective leaching.
The method used depends on the gold content as
well as on the type of impurities present.
While silver is soluble in both nitric and sulfuric
acids, and gold is insoluble, yet these acids
cannot be used to dissolve silver away from an
alloy containing more than 25% Au.
For high-gold alloys, aqua regia is therefore used.
In such alloys, gold is leached, while silver forms
an insoluble residue.
Gold is soluble in aqua regia, but a goldsilver
alloy containing more than 8% Ag cannot be
attacked due to the formation of an insoluble
layer of AgCl.
Therefore, the aqua regia leaching process is
used only for refining high-grade bullions, where
the silver does not amount to more than 8%, or
to cases where the bullion contains enough
copper to open it up to attack in spite of the
silver present.
In both cases, the bullion is first melted and
poured in water to obtain granules suitable for
leaching.
5
= = attacked attacked, x = not , x = not attacked attacked
Alloy
composition
[%]
Attack by
Alloy
Ag Au
HNO
3
or
H
2
SO
4
1
Aqua
regia
2
Remarks
Low-gold
bullion
100
75
0
25
x
x
Bullion treated by HNO
3
or H
2
SO
4
.
70
50
25
10
30
50
75
90
x
x
x
x
x
x
x
x
Bullion must be alloyed with Ag before treatment
with HNO
3
or H
2
SO
4
.
High-gold
bullion
8
0
92
100
x
x
Bullion treated by aqua regia.
Low
Low
-
-
gold alloys
gold alloys
In such alloys, silver is selectively leached. It
is necessary to alloy the bullion with silver
such that silver constitutes 75% of the alloy.
Such an alloy is known as parting alloy.
In the nitric acid process the reactions are:
3Ag + 4HNO
3
3AgNO
3
+ 2H
2
O + NO
3Cu + 8HNO
3
3Cu(NO
3
)
2
+ 4H
2
O + 2NO
6
melting
Au
residue
Washing Filtration
Drying
casting
of AgCl
Precipitation
Leaching
Cementation
Silver
AuAg parting alloy HNO3
Water
Gold
NaCl
Fe
The reaction is carried out in stainless steel vessels, and
nitric gases are oxidized and recovered as HNO
3
.
Silver and platinum will go into solution, while Au, Ru, Rh,
and Ir are left behind as a finely divided black mud.
Silver is recovered from the solution by precipitation as
AgCl by adding NaCl.
Silver chloride is then converted to metallic silver by
contact with scrap iron.
The gold residue is then washed, dried, melted, and cast
7
The introduction of sulfuric acid as a leaching agent
for refining gold reduced the cost greatly as compared
with the nitric acid process.
Cast iron vessels could be used, and copper in the
bullion is converted to copper sulfate, which is a
marketable product.
The process is shown in Figure 3 and the reactions
are:
2Ag + 2H
2
SO
4
Ag
2
SO
4
+ 2H
2
O + SO
2
Cu + 2H
2
SO
4
CuSO
4
+ 2H
2
O + SO
2
Solids
Siphoning
AuAg parting alloy H SO 2 4
Gold
Solids
Ag SO 2 4
Washing melting
Drying
casting
Filtration
Crystallization
Leaching
Silver
Water
Fe
Filtration
Crystallization
CuSO 5H O 4 2
Solution to waste
8
Silver, copper, and part of the palladium are dissolved, while Au, Pt, Ru, Rh,
and Ir are not.
The gold residue is separated, washed, dried, briquetted, melted, and cast.
The solution containing silver and copper is transferred to lead-lined tanks,
diluted with water, and cooled to crystallize Ag
2
SO
4
.
Silver sulfate is slightly soluble in cold water but dissolves readily in hot
concentrated H
2
SO
4
.
The crystals are separated, washed, reduced with scrap iron, melted, and cast.
The mother liquor is evaporated and cooled to crystallize and separate CuSO
4
.
The residual sulfuric acid is recycled. This process cannot be used for bullions
containing appreciable quantities of lead, because PbSO
4
will be left behind
with the gold residue and considerable fluxing of the final product would be
necessary to remove it.
High
High
-
-
gold alloys
gold alloys
Aqua regia is used to attack high-gold alloys since
both nitric and sulfuric acids are not effective.
In this method, gold, copper, and other impurities go
into solution while silver remains behind as silver
chloride. The leaching equations are:
2Au + 3Cl
2
2AuCl
3
(soluble)
2Ag + Cl
2
2AgCl (insoluble)
Cu + Cl
2
CuCl
2
(soluble)
9
The dissolving pans are made of stoneware, glass, or
fused silica and have a capacity of about 250 liters.
Each pan is filled two-thirds with HCl and heated by
steam injection. The nitric acid is added at intervals to
maintain a vigorous reaction.
The dissolution of gold follows the equation:
4HCl + HNO
3
+ Au HAuCl
4
+ NO + 2H
2
O
When the process is complete, the excess acid is
boiled off:
HNO
3
+ 3HCl NOCl + 2H
2
O + Cl
2
The liquor is allowed to settle, and the
supernatant solution is siphoned and treated
with a reducing agent (e.g., FeCl
2
, oxalic acid,
SO
2
) to precipitate gold, which is filtered off,
washed, and melted.
Silver chloride residues are washed with water,
and the first washings (containing gold) are
returned to the dissolving pan. The material is
then reduced with scrap iron to metallic silver.
10
Boiling
Aqua regia
Solids
AgCl
Leaching
Filtration
Gold
AuAg bullion
Settling Washing
Silver
Washing
Reduction
(Ag < 8%)
Cementation
Drying
melting
casting
Water Fe
Water
Solution
to waste
This process is of special value when
refining platiniferous gold.
Platinum and palladium are dissolved
together with gold, while Rh, Ru, and
Ir remain with the silver chloride.
Gold is precipitated by FeCl
2
, and
then filtered, and Pt and Pd are
recovered from the solution by the
usual methods.
11
Solvent extraction of gold
Solvent extraction of gold
Gold can be extracted from chloride
solutions by a number of organic
solvents. For example:
The Harmony Refinery
The Harmony Refinery
A sludge containing between 50 and 85% gold
was solubilized by leaching for 2 hours in
hydrochloric acid under chlorine gas stream.
The bulk of the base metals and platinum group
metals are also solubilized under these
conditions.
Silver precipitates as silver chloride and is
collected as a solid residue along with any silica.
This material can be treated in a separate
processing step to recover residual gold and
purify the silver.
12
The leach solution, containing about 65 g/L gold, is
treated by solvent extraction [the organic solvent
was not specified].
Gold is selectively extracted into the organic phase,
while all other metal ions report to the rafinate.
Small quantities of co-extracted impurities are
scrubbed from the loaded organic phase before it is
stripped to produce a purified, concentrated gold
solution.
The stripped organic phase is then recycled to the
extraction circuit. The HCI-rich rafinate from the
extraction section is returned to the leach, with a
small bleed to control the build up of base-metal
impurities in the leach/solvent extraction circuit.
13
Gold is recovered as a metal powder by
direct reduction from the loaded strip
liquor.
Use of gaseous sulfur dioxide as the
reducing agent produces gold meeting the
specification of 99.99% purity.
The leach and reduction are operated
batchwise, while the solvent extraction is
a continuous operation.
Equipment is mainly made of fiber-
reinforced plastic, polypropylene, and
high-density polyethylene.
14
ELECTROMETALLURGICAL ELECTROMETALLURGICAL
REFINING REFINING
In electrorefining technology the impure metal is cast in form of anode,
then dissolved electrolytically:
M M
n+
+ ne
The metal ion liberated at the anode migrates towards the cathode and
deposits on its surface.
The anodes cannot be dissolved completely, and between 10% and
30% of its weight remains at the end of the cycle as anode scrap.
The scrap is recycled. When soluble impurities can co-deposit onto the
cathode together with the metal to be refined, then the cathodes are
placed in diaphragm-equipped boxes.
The impure anolyte is withdrawn from the common anode
compartment, purified and returned to the cathode boxes.
Energy consumption is low because the anodic reaction is the same as
the cathodic.
The electrometallurgical route is conducted in
Wohlwill cell named after its German inventor Emil
Wohlwill.
Feed material is usually the anode slimes from silver
refining. These are collected, purified to remove
silver, and cast as anodes containing approximately
94% Au, 5% Ag, and 1% Cu, Pt, Pb, and Pd and
measuring about 20 x 10 x 1 cm.
Electrolysis is carried out in acidic chloride solutions
containing 150200 g/L Au and 140 g/L HCl at about
70C and at a current density of 1 200 A/m
2
, using
thin gold ribbon cathodes.
15
16
At the anode, the reaction
Au + 4Cl
[AuCl
4
]
+ 3e
Balbach
Balbach
cell
cell
These cells are mainly used in North America. They
consist of shallow tanks equipped with graphite or
stainless steel bottoms acting as cathodes.
The anodes are arranged horizontally above the
cathodes, resting on wooden frames with canvas
bags to retain the slimes.
Each cell is provided with only one anode and one
cathode. The cathode is a stainless steel plate
covering the entire floor area. Above this, at a
distance of 10 cm, is a slightly smaller framework of
nonconducting material, covered with fabric and
containing the anode.
The crude silver anodes are completely covered by
electrolyte. An advantage of this cell is that the
anode slime is recovered easily. Disadvantages
include the large space requirement and high energy
consumption.
Anodic sl imes
Anode basket
Anode bag
Cathode
Silver crystals
Electrolyte
Silver anodes
+
19
Moebius
Moebius
cell
cell
These cells are mainly used in Europe. In these
cells the anodes and the stainless steel cathodes
are arranged vertically.
Each anode is encased in a polypropylene or
canvas bag which collects the slimes. Electrolyte
mixing is accomplished by an oscillating cathode
scraper which also brushes the silver crystals off
the cathode plates.
The crystals are collected in a removable basket
with a filter cloth bottom, which is situated
beneath the electrode.
The cell voltage is 2.02.5 V and the energy
consumption is about 0.6 kWh/kg of silver.
20
+
Silver anodes
Cathodes
Electrolyte
Anode bag
Silver crystals
Mechani cal
scraper
+
21
The spent anodes are replaced continually by new
anodes, so that interruption of electrolysis is
necessary only if the electrolyte must be replaced
due to excessive copper concentration, or if the
anode bags have to be emptied. The electrolyte is
usually treated with copper to recover the silver by
cementation, and the copper is then recovered by
cementation with iron.
The process is most suitable for crude silver
containing > 90% Ag. With high copper content, the
electrolyte must be regenerated too often, and with
high gold content, the anode bags require frequent
emptying. Both are costly operations. A single
electrolysis gives a purity of 99.9599.99% Ag and a
double electrolysis gives a purity of 99.995
99.999%.
22
1
EXTRACTIVE METALLURGY OF EXTRACTIVE METALLURGY OF GOLD GOLD
8 8. Environment . Environment
Fat hi Habashi Fat hi Habashi
Laval University, Quebec City, Canada Laval University, Quebec City, Canada
Fathi.Habashi@arul.ulaval.ca Fathi.Habashi@arul.ulaval.ca
Pollution problems in the gold industry Pollution problems in the gold industry
arise from the following sources: arise from the following sources:
When gold is associated with When gold is associated with sulfide sulfide
minerals such as pyrite and minerals such as pyrite and arsenopyrite arsenopyrite
When amalgamation and When amalgamation and cyanidation cyanidation
processes are used for gold recovery processes are used for gold recovery
2
The treatment of The treatment of sulfide sulfide ores and ores and
cyanidation cyanidation process are well understood process are well understood
and can be well managed. and can be well managed.
Amalgamation process has been Amalgamation process has been
abandoned long ago because of the abandoned long ago because of the
toxicity of mercury but still used illegally in toxicity of mercury but still used illegally in
some tropical countries. some tropical countries.
Tailings from beneficiation of sulfide ores represent an
important disposal problem for the following reasons:
The presence of pyrite which undergoes aqueous oxidation
when exposed to weathering conditions generating sulfuric
acid:
FeS
2
+ H
2
O +
7
/
2
O
2
FeSO
4
+ H
2
SO
4
The acid generated will solubilize other minerals thus
releasing metal ions in solution.
3
The presence of traces of flotation reagents such as
xanthates, thiocarbamates, dithiophosphates, and organic
arsenic compounds.
Although the concentration of the collectors in the slurry is
in the parts per million range, but because of their toxic
nature they must be handled with care.
Terrains, hundreds of hectares, must be prepared to stock
pile this material either dry or under water.
Precautions must be taken to avoid breakage of the dams,
leaks, seepage to underground water, etc. Plantation of
mining waste and tailings dumps is becoming common to
improve the landscape.
4
Treatment of Sulfide Ores
When roasting is used for treating sulfides and arsenic
minerals to liberate the gold particles then SO
2
and arsenic
oxide must be captured and treated further.
If the exit gases are rich in SO
2
that are suitable for H
2
SO
4
manufacture, then the existence of a nearby market for either
the liquid SO
2
or the acid must be available.
Disposal of SO
2
can be achieved by absorption by CaO or
CaCO
3
to form CaSO
4
:
SO
2
+
1
/
2
O
2
+CaOCaSO
4
SO
2
+
1
/
2
O
2
+CaCO
3
CaSO
4
+CO
2
The difficulty with this suggestion is the requirement
and handling of large tonnage of solids; about three
tons of limestone have to be brought in and over four
tons of waste CaSO
4
have to be discarded for the
elimination of one ton of sulfur.
Another technology used today is treating these ores
in aqueous solution with oxygen at high temperature
and pressure in autoclaves to oxidize the sulfide
minerals, liberate the gold, render arsenic as a
harmless ferric arsenate in the residue, and precipitate
the sulfatesas gypsum.
5
Amalgamation
Gold ores were usually treated by the
amalgamation process to recover the large gold
particles.
The process is hazardous because of the toxicity
of mercury. Handling of mercury requires strict
man-agement to avoid its spilling and disposal in
streams, or emitting its vapour to the
atmosphere during the separation of gold from
the amalgam by distillation.
It has been completely eliminated except in the
Amazon region and other tropical countries
where it is still used illegally.
Cyanidation
Sodium and potassium cyanides have been
used for over a century to recover gold and
silver from their ores.
Cyanide solutions are highly toxic. Alkalinity
in cyanide leach solutions should be carefully
maintained to avoid the liberation of HCN into
the surroundings by atmospheric CO
2
:
2CN
+CO
2
+H
2
O 2HCN +CO
3
2
6
Bleed solution
It is common practice in cyanide mills to
dispose of a part of the cyanide from time to
time to prevent the accumulation of impurities
which may interfere with the leaching step.
This bleed solution should never be thrown
into the streams without prior treatment
because of its extreme toxicity.
7
Disposal of bleed solution
Oxidation of CN
to CNO
+Cl
2
+2OH
CNO
+2Cl
+H
2
O
Excess of chlorine oxidizes the cyanateion further to
CO
2
and nitrogen:
2CNO
+3Cl
2
+4OH
2CO
2
+N
2
+6Cl
+2H
2
O
Acidification to liberate HCN which is then absorbed
back in alkali to form alkali cyanide for recycle:
CN
+H
+
HCN
HCN +OH
CN
+H
2
O
8
Any copper and iron present in solution as
cyanides precipitate as copper ferrocyanide.
Remaining metal ions in the acid solution can
then be precipitated by Ca(OH)
2
and disposed
of safely.
1
EXTRACTIVE METALLURGY OF EXTRACTIVE METALLURGY OF GOLD GOLD
9 9. Gold from anodic slimes . Gold from anodic slimes
Fat hi Habashi Fat hi Habashi
Laval University, Quebec City, Canada Laval University, Quebec City, Canada
Fathi.Habashi@arul.ulaval.ca Fathi.Habashi@arul.ulaval.ca
An appreciable amount of gold is
An appreciable amount of gold is
obtained from the anodic slimes of
obtained from the anodic slimes of
silver, copper, and nickel
silver, copper, and nickel
electrorefining
electrorefining
.
.
2
Gold from silver electrorefining
Crude silver, from ores or from desilverization
and cupellation of lead generally has a purity of
9899.5%, which may include gold and
platinum-group metals whose value often
exceeds that of the silver itself.
Electrolysis is carried out in silver nitratesodium
nitratenitric acid electrolyte containing 150 g/L
Ag (pH 11.5) at a current density of 300 A/m
2
and a temperature of 35C.
Pure silver deposits on the cathode while gold
and platinum remain insoluble and are collected
in the slimes.
Two types of cells are used:
ThumBalbach cells
Moebius cells
3
ThumBalbach cells
Mainly used in North America.
They consist of shallow tanks
equipped with graphite or stainless
steel bottoms acting as cathodes.
The anodes are arranged horizontally
above the cathodes, resting on wooden
frames with canvas bags to retain the
slimes.
ThumBalbach cells
4
Each cell is provided with only one anode and one
cathode. The cathode is a stainless steel plate
covering the entire floor area.
Above this, at a distance of 10 cm, is a slightly
smaller framework of nonconducting material,
covered with fabric and containing the anode.
The crude silver anodes are completely covered by
electrolyte.
An advantage of this cell is that the anode slime is
recovered easily. Disadvantages include the large
space requirement and high energy consumption.
Moebius cells
Mainly used in Europe.
In these cells the anodes and the stainless steel
cathodes are arranged vertically.
Each anode is encased in a polypropylene or
canvas bag which collects the slimes.
Electrolyte mixing is accomplished by an
oscillating cathode scraper which also brushes
the silver crystals off the cathode plates.
The crystals are collected in a removable basket
with a filter cloth bottom, which is situated
beneath the electrode.
5
Moebius cells
Gold from copper electrorefining
Raw copper (blister) obtained by smelting
copper sulfide concentrates is about 97% pure.
It undergoes fire refining to remove as much as
possible of the sulfur and oxygen before casting
in form of anodes for electrolytic refining.
The anodes (weighing 300380 kg) are
transported to the tankhouse, where electrolysis
is carried out.
6
Any gold present in the anodes will
detach together with other insoluble
impurities and collect at the bottom of the
cell in form of slimes.
The slimes are mainly the precious metals
and their compounds with selenium and
tellurium as well as some Cu
2
S, Cu
2
Se,
and Cu
2
Te. They constitute 5 to 10
kg/tonne of the anodes.
A number of processes are available for the
treatment of these slimes to recover their
precious metal content as well as selenium
and tellurium.
The old technology involving baking with
concentrated sulfuric acid at about 300
o
C
has been abandoned because of pollution
problems with SO
2
generated.
A pressure leaching process is now used in
some plants
7
Pressure leaching process
Another process using the top blown rotary
converter is also used. In this process
oxygen is introduced by means of a lance
from the top opening.
The combined action of oxygen and rotation
enhances the oxidation reaction in the
molten bath resulting in the volatilization of
selenium and tellurium. Gold and silver
remaining in the converter are then cast as a
bullion for further refining.
8
Top blown rotary converter
Gold from nickel electrorefining
Nickel anodes for the electrolytic process are
supplied from the following sources:
Metal produced by reduction of NiO with
petroleum coke at 1540C; typical analysis 94%
Ni, 1% Co, 4% Cu, and small amounts of other
impurities. This process is used by INCO.
Metal produced by reduction of nickel oxide
copper oxide analyzing 76% Ni, 1.5% Co, 17%
Cu, and other impurities. This process is used by
Falconbridge
9
Nickel refining is usually carried out from a mixed
sulfatechloride system because it has a higher
conductivity which results in a lower cell voltage, and in
permitting the use of chlorine for electrolyte purification.
The principal impurities from the anode such as iron,
cobalt, lead, arsenic, and copper go into solution with the
nickel.
Silver, gold, the platinum group metals, sulfur, selenium,
and tellurium fall to the bottom of the cell as an insoluble
slime which are collected, melted, and cast into anodes
enriched in precious metals which are processed for
recovery.
To avoid contamination of the refined nickel cathodes
with soluble impurities, special cells known as
Hybinettecells are used.
The purified solution is returned to the cathode
compartment, which is separated from the anode by a
porous disphragmin the form of a box enclosing the
cathode, at such a rate that a hydrostatic head of
solution builds up relative to the rest of the
electrolyte.
This prevents impurity ions from diffusing into the
cathode compartment.
10