Chapter 7 CHEMISTRY OF THE CIP PROCESS Richard E Browner

____________________________________________________________________

INTRODUCTION

Gold, the only yellow metal, derives its name from the old English
word Geolu meaning yellow. Its chemical symbol Au is from the
Latin word for gold, Aurum.

Atomic No 79
Atomic wt 197
Density 19.32 g cm-3

The units used to describe gold content and purity are numerous.
The ore is usually referred to in grams per tonne or ounces per
tonne where

1 gram = 0.03215 ounces (troy).

Assay values are given in parts per million by weight which are
equivalent to grams per tonne.

Bullion is expressed as fineness, that is, parts per thousand. For

example the Australian nugget gold coins have a fineness of 999.9.

Caratage is used when the gold is alloyed with another metal.

Twenty-four carat is pure gold or 1000 fine. The proportion of 24
gives the gold content by weight.

Figure 7.1 World gold supply 1989: 1948 Tonnes

Brazil Other Africa
USSR Sales
3%
5% 15%
Other Latin America 7%
Europe 1
Other Asia 2
Philippines 2
Other Oceania 1
PNG 2

Australia 10%
31%

South Africa
8%
Canada

13%
USA

7.1
 The world gold supply for 1989 is shown in figure 7.1 and the
world gold demand for the same year is shown in figure 7.2.

Figure 7.2 World gold Demand 1989: 1948 tonnes

Medals
1%
Investment
19%

Industry
9%

Coins
Jewellery 5%
66%

This chapter will look at the chemistry of the extraction of gold by

the CIP process. We will progress through the unit processes found
on a typical CIP plant;

1) leaching,
2) carbon adsorption,
3) elution,
4) electrowinning,
5) smelting
6) carbon regeneration.

7.2
LEACHING

The CIP/CIL process as used today is a relatively new technology

with the first full scale plant being commissioned in 1973.

HISTORY OF GOLD LEACHING

Pre 1890 - Chlorine/Chloride - Zinc cementation.

1880 - Davis patented wood charcoal to

recover gold from chlorinated solutions.

1891 - Davis process used at Mount Morgan,

Australia.

1887 - MacArthur and Forrest Brothers used

cyanide to dissolve gold.

1889 - First commercial use of cyanide -

Crown Mine, New Zealand.

1894 - Johnson patented use of wood charcoal

for the recovery of gold from
cyanide solution.

1916 - Gold extraction using carbon at Yuanmi

Mine, Australia.

1939 - Chapman patented flotation of carbon

after adsorption.

1950 - Fruit pit carbon used experimentally,

Getchell Mine, Nevada, USA.

1952 - Zadra elution process developed.

1973 - Carbon-in-Pulp introduced at

Homestake Mine, South Dakota, USA.

Developed from Marsden and House (1992) and McDougall

(1991).

7.3
pH Potential Diagrams

Figures 7.3 and 7.4 show the stability fields for gold species as a
function of Eh and pH. Figure 7.3 is for the gold water system.
The dashed lines are the boundaries of the stability region of water.
An oxidising potential can be applied by a variety of oxidising
agents. Some common ones being oxygen in air or pure oxygen,
hydrogen peroxide, chlorine, etc.

It can be seen from figure 7.3 that an oxidising potential in excess

of 1 at a pH of 8 is required to dissolve gold. Unfortunately this is
greater than the potential required to decompose water.

The addition of cyanide produces a stable gold cyanide species,

Au(CN)2-. Figure 7.4 shows the region where gold can be leached
by a cyanide solution to form gold cyanide.

Figure 7.3 Figure 7.4

From the gold-cyanide Eh-pH diagram it can be seen that gold will
leach from a pH of 0 to 14. The lowest Eh value occurs at a pH of
about 10.5. This corresponds to maximum cyanide as CN- and not
HCN.

7.4
DISSOLUTION OF GOLD:
When gold dissolves in a cyanide solution it does so by the
reaction:

GOLD + SODIUM + OXYGEN + WATER Û GOLD + CAUSTIC

CYANIDE CYANIDE SODA

4 Au + 8 CN- + O2 + 2 H2O = 4 Au(CN)2- + 4 OH-

From this equation it can be seen that in order to dissolve gold

oxygen and water as well as cyanide are required.

The gold present in many gold ores will dissolve in cyanide

solutions without any problems. These are called non-refractory
ores and are usually oxidised ore that consist mainly of minerals
that do not react with cyanide such as quartz and other silicates.

Ores that contain gold that does not dissolve readily in cyanide
solutions are called refractory ores. There are many types of
refractory ores. One major type is where the gold is locked in a
mineral such as pyrite and the cyanide solution can not reach the
gold to dissolve it. These ores need to be roasted to disrupt the
pyrite structure and allow the cyanide solution to reach the gold.

Another major type of refractory gold ore are those which contain
minerals that will also react with the cyanide. These minerals
(pyrrhotite, chalcopyrite, pyrrhotite, etc) are known as cyanide
consumers, cyanocides or cyanicides.

CYANICIDES:

1. Copper Minerals:

Copper minerals such as Chalcocite (Cu2S) and

covellite (CuS) dissolve in cyanide solutions and cause
excessive consumption of cyanide. This slows down
the dissolution of gold as there is less cyanide at the
gold surface to dissolve the gold.

CuS + H2O + 4CN- Û CuCN42- + SCN- + 2OH-

Covellite + water + cyanide Û copper cyanide + thiocyanate + hydroxide

2. Sulphide Minerals:

Some reactive sulphide minerals such as marcasite and

pyrrhotite will dissolve in cyanide solutions. The effect
is the same as that for copper minerals.

3. Flotation Reagents: (Copper sulphate):

Copper added in the form of copper sulphate as a

flotation reagent will react with cyanide and consume it.

7.5
RATE OF DISSOLUTION OF GOLD:
The rate or speed at which gold will dissolve depends on many
variables. Firstly the gold must be liberated so that the cyanide
solution can reach the gold particles. Once this is achieved the
following factors also play and important part in the speed of
leaching.

1. Coatings:

Gold can be coated with a variety of substances that cause

the gold to dissolve much slower. Iron oxides or tarnish,
clay and elemental sulphur may coat gold. Flotation
reagents designed to coat minerals and make them water
repellent so they float can also coat gold particles and
make them water repellent which will also repel the
cyanide solution reducing the rate at which the gold will
dissolve.

2. Size of Gold Particles:

The rate that gold particles dissolve depends directly on

their size. Larger particles take longer than smaller
ones. This is why coarse gold is often separated by
gravity methods before the remainder of the ore is sent
to cyanidation.

3. Gold Compounds:

Compounds of gold can dissolve slowly in cyanide

solutions. Gold tellurides dissolve very slowly and
often require a roasting or chlorination step prior to
cyanidation.

4. Cyanide:

At low cyanide concentration, cyanide can be the limiting

reagent that slows down the leaching of gold. This usually
is not the case in CIP circuits where a large excess of
cyanide is usually used.

5. Oxygen:

Oxygen is normally the reagent that limits the rate at

which gold will dissolve. CIP leach tanks need to be kept
well oxygenated by sparging with air or oxygen.

6. Temperature:

The rate that gold will dissolve in cyanide solutions

increases with increasing temperature up to about 85oC. It
then begins to decrease due to less oxygen being dissolved
in hot solutions.

7.6
CYANIDE SOLUTIONS:
When solid sodium cyanide dissolves in water, some of it will react
with the water to form hydrogen cyanide gas (HCN):

SODIUM + WATER Û HYDROGEN + CAUSTIC

CYANIDE CYANIDE SODA

NaCN + H2O Û HCN(g) + NaOH

How much hydrogen cyanide gas is formed will depend on the

acidity of the water. The lower the pH or the more acidic the water,
the more hydrogen cyanide gas is formed.

Some highly saline bore water can have a high acid content with a
pH as low as 4. Water that has an acid nature needs to be
neutralised or made alkaline before sodium cyanide is added. Lime
or caustic soda is usually added to adjust the pH and make the
water alkaline.

The following diagram demonstrates the percentage cyanide, as

hydrogen cyanide gas as a function of pH in fresh water. If excess
aeration occurs or the pH is allowed to drop, HCN(g) will be
formed and cyanide lost.

100 0
90 10

% cyanide as HCN gas

80 20
-

70 30
60 40
% cyanide as CN

50 50
40 60
30 70
20 80
10 90
0 100
4 5 6 7 8 9 10 11 12 13 14
pH

Figure 7.5 Cyanide ion as a function of pH in fresh water.

From figure 7.5 it can be seen that a pH in excess of 10 is required

to keep most of the cyanide in solution as the hydrogen cyanide ion
(CN-). A pH of 10.5 is typically used in a CIP plant. If the plant is
using saline water, lower operating pH values of about 9.0 can
often be used. The pH is increased to higher values by adding
alkalis.

7.7
ALKALIS:
Alkalis are substances that make water basic or alkaline. By
removing acid and producing alkalinity they can prevent the
formation of hydrogen cyanide gas. Common alkalis used in the
CIP process are quicklime (calcium oxide), hydrated lime (calcium
hydroxide) and caustic soda (sodium hydroxide).

In addition to preventing the loss of cyanide as hydrogen cyanide

gas, alkalis also:

a) Neutralise acid constituents in mill water and ore before

addition to cyanide circuit.

b) Aid in extraction of gold from tellurides which

decompose more readily at highly alkaline solutions.

WATER:

Many gold operations in arid areas use saline bore water in their
treatment plants. This salt water can have up to 250000 ppm total
dissolved salts or 6 times the salinity of sea water. It is saturated
with dissolved salts and very easily forms solid salts.

The two main salts present are sodium chloride, or common salt
(~90%) and magnesium sulphate, or magnesia (~10%).

The sulphate in the salt water reacts with calcium from lime or the
ore to form calcium sulphate (gypsum). Most of the scale in pipes
and on screens is due to gypsum. This problem may be reduced by
using caustic soda instead of lime for protective alkalinity.

CALCIUM MAGNESIUM CALCIUM MAGNESIUM

HYDROXIDE + SULPHATE = SULPHATE + HYDROXIDE
(LIME) (GYPSUM)

Ca(OH)2 + MgSO4 = CaSO4(s) + Mg(OH)2

The magnesium present in salt water usually prevents the pH of the

process water from raising above a pH of 9.0 to 9.2. At about this
pH the solution usually consumes all extra alkali added to form
magnesium hydroxide.

MAGNESIUM + SODIUM = MAGNESIUM + SODIUM

SULPHATE HYDROXIDE HYDROXIDE SULPHATE
(SOLID)

MgSO4 + NaOH = Mg(OH)2 + Na2SO4

7.8
 Figure 7.6 shows a typical pH rise for saline water as an alkali
reagent such as lime is added. At a pH of about 9.0 to 9.2 the pH
stops increasing as more alkali is added.

Figure 7.6 pH Modification of Salt Water with an alkali.

7.9
 OXYGEN:

At cyanide concentrations above 2.5 x 10-3 mol dm-3 the rate of

leaching is controlled by the transfer of oxygen to the gold surface.
The solubility of oxygen (5-10 mg dm-1) in water therefore plays an
important part in gold leaching. A variety of minerals will remove
oxygen from a leach solution. The most common are arsenic
minerals and reactive sulphides such as pyrrhotite. Naturally
occurring organics such as lipids and humates can also consume
oxygen. Oxygen consumers can be overcome by using one or more
stages of air, oxygen or hydrogen peroxide pretreatment, prior to
the introduction of cyanide.

The use of oxygen and peroxides in gold leaching is becoming

accepted. Hoeker (1992) indicates that about thirty gold plants in
Australia are using oxygen injection. The claimed benefits of using
oxygen include:

Increased gold recovery.

Reduced residence time.

Reduced cyanide consumption.

Lower cyanide levels required.

Lower operating costs compared with compressed air.

Figure 7.7 shows the rate of gold dissolution for a given oxygen
concentration in the aeration gas being bubbled through the
solution.

14

12
Rate of gold dissolution mg/sq.cm/hour

10

0
0 10 20 30 40 50 60 70 80 90 100
Oxygen / %

Figure 7.7 Rate of gold dissolution versus oxygen concentration. Data from
American Cyanamid Company, 1968.

7.10
Table 7.1 gives the maximum effective oxygen concentrations for
given cyanide levels (Nicol, Fleming and Paul 1987).

Table 7.1. Maximum effective oxygen concentration at various

cyanide levels

NaCN concentration / % Oxygen concentration / mg/l

0.005 3.2
0.01 6.5
0.02 13.1
0.03 19.6
0.04 26.1

Table 7.2 summaries the oxygen addition options, which are

available to maintain oxygen levels in the pulp to reasonable
values.

Table 7.2. Summary of use of different oxygen supplements and

plant observations (After La Brooy, Muir and Komosa 1991).

Air (Max. O2 concentration 9 mgL-1)

Can strip HCN(g) from the solution especially at
pH about 9.2 with saline water.
Oxygen (Max. O2 concentration 40 mgL-1)
Accelerates leaching kinetics. Cyanide savings in
the presence of reactive sulphides. Reduced
Pb(NO3)2 requirements.
CILO (Max. O2 concentration 25-40 mgL-1)
Accelerates leach kinetics. Cyanide savings in 5h
lab test. No Pb(NO3)2 required.
H2 O2 (Max. O2 concentration 40 mgL-1)
Accelerates leach kinetics. No stripping of
HCN(g) from solution. Degussa PAL application
rate 0.2-0.5kgt-1. Less copper leaching, reduction
in cyanide consumption with increase in gold
recovery.
CaO2 (Max. O2 concentration 40 mgL-1)
Accelerates leach kinetics more than recovery.
No stripping of HCN from solution. Active in
heap leach for > 20 days. Maximum O2 release at
pH 9. Application rate 0.1-0.8kgt-1.

7.11
CARBON ADSORPTION

ACTIVATED CARBON

HISTORY

Egyptians - Purifying agent

Ancient Hindus - Filter drinking water

1847 First recorded use to adsorb gold from chloride

solutions.

1880 Davis patented wood charcoal to recover gold

chloride.

1890 MacArthur and Forrest Brothers found cyanide

was a good solvent for gold.

1894 Johnson patented wood charcoal to recover

gold cyanide.

1917 Wood charcoal in columns, Yuanmi Mine, WA,

Australia.

1961 First fully integrated CIP Plant, Cripple Creek,

Colorado, USA.

Developed from Marsden and House (1992) and McDougall

(1991).

STRUCTURE

Activated carbon is a very porous carbon based product based on a

graphite structure. The normal structure of graphite is shown
below.

Figure 7.8 Schematic representation of the structureof graphite (after

Bochris, 1969).

7.12
 Activated carbon is formed when part of the graphite structure is
burnt away leaving a very porous product.

Figure 7.9 Schematic representation of the proposed

structure of activated carbon.

During activation, functional groups are formed along the edges of

the broken graphite planes. These functional groups serve the
purpose of rendering the carbon hydrophilic. The carbon will
therefore be wetted by water and gold cyanide adsorbed from
solution.

Figure 7.10 Structure of some surface oxides:

(a) carboxylic acid (b) phenolic hydroxyl
(c) quinone-type carbonyl groups (d) normal lactone
(e) fluorescein-type lactones (f) carboxylic acid anhydrides (g) cyclic
peroxides (after Mattson and Mark, 1971).

7.13
MANUFACTURE OF ACTIVATED CARBON:
Activated carbon can be manufactured out of numerous materials.
Some materials include: coal (peat, lignite, bituminous coal or
anthracite), coconut shells, peach and apricot pits, wood, etc. The
physical characteristics, structure and pore size distribution of the
resultant carbon are determined by the type of raw material used.
Activity of the carbon is determined by conditions used in the
manufacturing process.

Coconut shell activated carbon is most often used in the adsorption

of gold cyanide from solution. A flow sheet for its manufacture is
shown below.

Raw coconut shell

Carbonisation

Optional
crushing/screening

Activation

Cooling

Crushing/screening

Bagging

Figure 7.11 Flowsheet for the manufacture of activated carbon

from coconut shells (after Yehaskel, 1978).

The carbonisation step involves heating the carbon in an inert

atmosphere to about 600oC. In this process volatile components in
the coconut shell are driven off producing a char.

7.14
 Activation is conducted by heating the char to between 800 and
1100oC in the presence of steam, air, carbon dioxide or a
combination of these. Preferential etching occurs, removing weak
spots in the char, and creating a large internal surface area.

WOOD CHARCOAL 2-4 m 2 / gram

THERMAL
ACTIVATION

ACTIVATED CARBON
1000 m2 / gram

Figure 7.12 Surface area increase during activation.

A surface area in excess of 1000 m2g-1 may be produced. This is

the primary advantage of activated carbon over wood charcoal.
Both when activated have the same activity per square metre of
surface area but activated carbon has a much larger surface area.

To achieve maximum adsorption, the pores in the activated carbon

used for gold cyanide adsorption should be larger than the gold
cyanide molecule to allow easy access but small enough to allow
maximum pore volume. A pore size distribution is shown below
for coconut shell and coal-based carbons. The gold cyanide
molecule fits easily into the majority of coconut shell carbon pores
shown at about 10Å radius.

Figure 7.13 Pore size distribution for a typical thermally activated

coal-based carbon and a coconut shell-based carbon (after Fornwalt
et al., 1963).

7.15
ADSORPTION OF GOLD CYANIDE ONTO ACTIVATED CARBON:

No consensus has been achieved amongst researchers regarding the

mechanism by which gold cyanide loads onto activated carbon.
One proposed method of adsorption will be examined. This
method, although not universally accepted, aids in the
understanding of fouling of activated carbon and other processes
that occur in the CIP/CIL circuit.

Ion-pair adsorption

Au(CN) -2
Carbon
CaAu(CN) 2

Ca2+

Mg 2+

Figure 7.14 Proposed mechanism of ion pair adsorption.

According to the ion-pair adsorption theory, a cation forms a bond

with the negatively charged gold cyanide ion which is then
adsorbed onto the carbon particle. From the ion-pair mechanism, it
can be seen that:

1) the loading capacity of activated carbon will increase

with increasing concentration of cation in the order

Ca2+ > Mg2+ > H+ > Li+ > Na+ > K+

2) anions in solution will decrease the loading capacity of

activated carbon with increasing concentration in the
order

CN- > S2- > SCN- > SO32- > OH- > Cl- > NO3-

Nicol et al. (1987).

It is thought that anions such as CN- compete with gold cyanide for
active sites on the carbon.

7.16
FOULING OF ACTIVATED CARBON:

Carbon is said to be fouled when substances other than gold

cyanide have adsorbed onto the carbon preventing gold cyanide
from adsorbing. Fouling of carbon can be classified into two types.
Inorganic fouling by substances such as calcium carbonate, silica
and magnesium hydroxide and organic fouling by oil, flotation
agents and other organic molecules.

Fouling by inorganics

Many anions other than gold cyanide will form ion-pairs and adsorb
onto activated carbon, competing with gold cyanide for active sites.

Mg(OH)2

CaCO3
Fe(CN)6
Carbon

Silica

Figure 7.15 Fouling of activated carbon by inorganics.

A second mechanism by which inorganics can deactivate carbon is

by precipitation in pores reducing the available surface area.
Calcium carbonate is believed to act in this way. Haematite, silica
and finely divided clay and shale material may also lodge in pores,
block them, and reduce the surface area available for gold cyanide
adsorption.

7.17
Fouling by organics

Fouling by organics can be divided into two groups. The following

tables (after La Brooy et al., 1986) show the effect of organics on
carbon. The first table shows the effect of large organic molecules
on carbon. These molecules are assumed to be too large to enter
the pores on the carbon used for gold cyanide adsorption. As a
result they adsorb mainly on the outside surface of the carbon
particle not significantly reducing the surface area or activity of the
carbon.

Organic reagent % activity vs distilled water,

(@ 20 ppm unless stated) after ageing

Calgon Pica
GRC 22 G210 AS

Control
Distilled water 100 100

Grinding aid

Dow XFS 4272.00 (10 ppm) 102

Viscosity modifiers

Sodium pyrophosphate (2 x 10-3 M) 94

Sodium hexametaphosphate, 84
'Calgon' (130 ppm)

Freevis 528 117

Flocculants

Magnafloc E24 88

Cyanamid A2120 88

Table 7.3 Fouling of carbon by large molecule (after La Brooy et al., 1986).

Small organic molecules can, however, penetrate into the pores of

the activated carbon used to adsorb gold cyanide and block them.
Small organic molecules such as oils, frother, and collectors are far
more detrimental to a CIP/CIL circuit than larger organic
molecules.

7.18
Collectors
Sodium ethyl xanthate 44

Sodium iso-butyl xanthate 22

Potassium amyl xanthate 6

Aerofloat 208 42

Frothers

Teric 401 17 17

Teric 402 22 25

Dowfroth 200 20 24

MIBC 42 32

Oils

Mobil ALMO 527 31

Diesel 30

Multigrade 14

Vegetation products

Swamp water 19 13

No ageing
Standard kinetic test 188 190

Table 7.4 Fouling of carbon by small organic molecule

(after La Brooy et al., 1986).

7.19
CARBON REACTIVATION (REGENERATION):

The reactivation of carbon takes two forms. Inorganic foulants can

be removed by acid washing in a 3 to 10% hydrochloric acid
solution prior to elution. Organic foulants have to be burnt away.
This is usually done in a rotary or vertical kiln at temperatures
between 600 and 750°C. During kiln regeneration, a small part of
the carbon is burnt away releasing haematite and silica that may
have lodged in the pores and deactivated the carbon. The surface of
the carbon is also reactivated in the kiln regeneration step.

FOULANT SOURCES REACTIVATION

1. Calcium carbonate Lime, ore, water Acid wash

2. Magnesium hydroxide Water Acid wash

3. Silica Lime, ore Kiln

4. Iron oxides, cyanides Ore calcine Acid wash

5. Copper compounds Flotation, ore Acid wash

6. Organics Flotation, wood, Kiln

oils, etc.

Table 7.5 Some carbon foulants, and suggested means of removing them.

7.20
ELUTION OF GOLD FROM CARBON:

Gold cyanide at concentration used in CIP/CIL plants is physically

and reversibly adsorbed onto activated carbon. Physical adsorption
is a thermodynamically reversible process that can be reversed by
disruption of the equilibrium between gold in solution and gold on
the carbon.

High gold cyanide and cation concentrations, low temperatures, low

anion concentrations and active carbon drive the gold cyanide onto
the carbon. During elution, lack of cations (Ca2+, Mg2+, etc), high
anion concentration (CN-, OH-) and high temperatures will disrupt
the equilibrium and remove gold cyanide from the carbon.

Figure 7.16 Effect of the concentration of hydroxide and cyanide in

the eluant on the elution rate (after Adams and Nicol, 1986).

While an increase in hydroxide and cyanide will increase the rate of

elution, an increase in cation concentration will decrease the rate of
elution.

7.21
Figure 7.17 The effect of the ionic strength of the eluant (NaCl) at
the eluant rate (after Adams and Nicol, 1986).

The most critical factor in the elution of gold cyanide from

activated carbon is temperature. Thermodynamically the
equilibrium loading on activated carbon will be decreased with
increasing temperature. The rate of kinetics of elution also
increases with increasing temperature.

Figure 7.18. Effect of temperature on the rate of gold extraction

(after Fleming and Nicol, 1984).

7.22
 Optimum elution can be achieved by high temperatures, high anion
(hydroxide and cyanide) concentrations, low cation (Mg2+, Ca2+,
etc.) concentrations and low gold cyanide concentrations in
solution.

A problem is encountered when cyanide decomposes rapidly at

elevated temperatures.

Figure 7.19 The decomposition rate of cyanide

in aqueous solution as a function of temperature
(after Adams and Nicol, 1986).

CN- + 2 H2O Û NH3 + H CO2-

H CO2- + OH- Û CO32- + H2

CO32- + H2O Û CO2 + 2OH-

The decomposition rate of cyanide and the subsequent detrimental

effects on elution can be minimised by adding cyanide continuously
throughout the elution cycle.

7.23
 Build-up of gold cyanide in the eluant will also decrease the rate of
elution.

Figure 7.20 The effect of gold in the eluant feed on the rate of elution
(after Adams and Nicol, 1986).

Several methods have been developed to minimise the effects of

gold build-up in the eluant. These will be examined as we have a
look at three elution processes: Zadra, AARL and Micron elution
procedures.

7.24
Zadra Elution Process

1% NaOH
0.2-1% NaCN
95-100 oC pH ~ 13
atmospheric Elution
100-150 oC
pressure

Electrowinning

80-90 oC

Figure 7.21 Flowsheet for the Zadra elution process.

This elution procedure was developed by Zadra at the U.S. Bureau

of Mines in the early 1950's. A hot aqueous solution of 1% sodium
hydroxide and 0.2 - 1.0% sodium cyanide (3-4 k litres per tonne of
carbon) is circulated through the carbon, to an electrowinning cell,
and back through the carbon. Gold cyanide build-up in the eluant is
prevented by circulation through the electrowinning cell. Most
Zadra circuits operate at atmospheric pressure and 95-100oC with
times usually ranging between 30 and 48 hours for stripping of the
carbon.

As temperature is such a critical parameter, increasing the

temperature above 100oC will greatly aid elution. Pressurised
Zadra circuits have hence been introduced. These operate at 5-6
atmospheres and 150oC. Elution can be achieved in as low as 6
hours.

Flow rate through the elution column is not critical. A flow rate of
about 1-2 bed volumes per hour seems to be reasonable for a Zadra
elution circuit. If a low length to diameter elution column is used,
care must be taken to avoid channelling in the column.

Zadra elution has the advantage that it requires smaller volumes of

potable water than does the AARL elution process. A bleed off
about 33% eluant can be done to limit the build-up of ionic strength
in the circuit.

7.25
Anglo-American elution procedure (AARL)

1-3%NaOH Demin
2-5%NaCN Water
100
to
o Elution
120 C

Electrowinning

40- 60o C Diluted NaOH

Diluted NaCN

Variable flow rate

Figure 7.22 Flowsheet for the AARL Process.

The loaded carbon is pre-soaked with 0.5-1 bed volume at hot 2-5%
sodium cyanide and 1-3% sodium hydroxide for about 1 hour.

The procedure can be operated at atmospheric pressure and 95-

100oC or at a slightly elevated pressure and 110oC; elution is
complete in 8-12 hours at 110oC.

Pre-soaking is followed by elution with pure water (about 8 bed

volumes) at a flow rate of 2 bed volumes per hour.

This is a batch process and the spent eluant is not recycled after
electrowinning.

If fresh water is at a premium, the AARL process can be run as a

"split" elution. In this variation, only the first four bed volumes of
eluant advance to electrowinning. The last four bed columns,
which contain only a low gold tenor, are stored in an intermediate
tank and used in the next elution. This has the advantages of
reducing water usage, heating costs and electrowinning capacity.

The AARL process relies on the strong influence of the ionic

strength to desorb the gold cyanide from the carbon. The rate of
desorption increases as water quality improves; cations are
decreased.

7.26
 Figure 7.23 Effect of different cyanide cations
on the rate of desorption of gold
(after McDougall et al., 1980)

Elution with Organic Solvents

2% NaOH
10% NaCN

80oC

Methanol

Electrowinning

NaOH
NaCN

Figure 7.24 Flow sheet of the Micron Elution Process.

7.27
The loaded carbon is firstly soaked in a solution of caustic soda
(2%) and sodium cyanide (10%) at a temperature of 25oC.
Methanol is then refluxed through the carbon from a hot still below
the column. The condensed methanol carries the desorbed gold
back to the still. Elution is complete in 4-6 hours and a very
concentrated eluant is produced which makes the electrowinning
procedure fast and effective.

The advantages of this system are the low usage of high quality
water and the production of a stripped carbon free of organic
contaminants such that kiln reactivation is not required for periods
up to 6-12 months. Hence for projects with limited upfront capital,
this system may be preferred. A kiln can be fitted after a year when
a cash flow is established. The running costs of a Micron system
are, however, much higher than ZADRA or AARL (Kyle 1987).

Figure 7.25 Comparison of elution procedures with

extruded and coconut carbon
(after Muir et al., 1984)

7.28
REGENERATION / REACTIVATION OF ACTIVATED CARBON
The organic molecules that adsorb on carbon reducing its activity
need to be removed. Activated carbon is, therefore, periodically
subjected to thermal treatment to selectively remove the organic
adsorbates and thus restore its activity.

REGENERATION STEPS

The following steps (Van Vliet 1991) occur when fouled carbon is
heated in a regeneration kiln.

0-200oC Drying which eliminates water and highly

volatile adsorbates.

200-500oC Vaporisation of volatile adsorbates, and

decomposition of the unstable adsorbates to
form volatile fragments.

500-700oC Pyrolysis of the non-volatile adsorbates that

results in the deposition of a carbonaceous
residue on the surface of the activated carbon.

700oC Selective oxidation of the pyrolysed residue by

steam, carbon dioxide, or a combination of
oxidising agents.

7.29
 ACTIVATED CARBON LOSS

Calcium, magnesium and iron are known catalysts for the steam
carbon gasification reaction. Acid washing before kiln regeneration
removes most of the calcium and some of the magnesium and iron
thus reducing the amount of carbon that is lost in kiln regeneration.

THE EFFECT OF ACID WASHING ON CARBON QUALITY

Regeneration temperature (30 min contact time

+ steam)
Test parameters measured 750oC 800oC 850oC
Mass loss, %
Acid wash before 0.36 3.15 3.25
regeneration
Acid wash after regeneration 0.73 3.14 6.23

Attrition* resistance, %
Acid wash before 0.9 1.0 1.7
regeneration
Acid wash after regeneration 1.8 1.4 2.6

Kinetic Activity+, %
Acid wash before 52 (43) 53 (48) 56 (56)
regeneration
Acid wash after regeneration 51 (50) 51 (53) 56 (56)

Carbon capacity for gold+, kg/t

Acid wash before 20 (18) 20 (18) 19 (19)
regeneration
Acid wash after regeneration 24 (17) 24 (17) 24 (17)

* Attrition was measured after 5 days by use of the standard AARL procedure
+ Kinetic activity and carbon capacity were measured by use of AARL
procedures both before and after extended attrition

Table 7.6 The effect of acid washing on carbon quality

(after Davidson and Schoeman, 1991)

7.30
REACTIVATION TEMPERATURE VS CARBON ACTIVITY

The optimum temperature for kiln regeneration depends on the type

of organic foulants on the carbon. If no flotation reagents, frothers
or organics are present regeneration at 600°C is satisfactory. In the
presence of organic agents and vegetation decomposition products,
temperatures of up to 750°C are required. The following graph
shows the effect of reactivation temperature on carbon activity.

450

400

350
Carbon activity (k)/hr-

300

250

200

150

100

50

0
300 400 500 600 700 800 900
Reactivation temperature/ C

Figure 7.26 Laboratory study of carbon activity

vs reactivation temperature.

A reactivation temperature about 750°C will not greatly increase

the activity of the carbon. A higher temperature will burn away
more of the activated carbon, making the structure weaker. Thus
breakdown of the carbon is more likely to occur with the resultant
loss of gold on the fine carbon. The temperature needed to achieve
reactivation will depend on the type of organic material fouling the
carbon.

7.31
 CARBON REGENERATION AT VARIOUS CARBON-BASED PLANTS

Regeneration conditions
Pre-acid Pre- Carbon Approx.
Circuit wash drying Kiln temp. /°C residence time
(Yes/No) (Yes/No) type at temp. min
Ergo Yes Yes Rotary 730 40
Simmergo No No Rotary 650 15
Daggafontein Yes Yes Rotary 700 20

New Brand Yes No Rotary 600-650 NA

Brand Calcine Yes No Rotary 660-730 NA

City Deep Yes Yes Rintoul 700 30

Crown Mines Yes Yes Rintoul 700-750 90
Crown Mines Yes No Rotary 750
Harmony Yes Rintoul 700 60
Western No No Rotary 600-650
Areas
Doornkop No No Rotary 720 10

Grootvlei Yes No Rotary 650

Beatrix No Yes Rotary 600
St Helena No No Rotary 710
Kinross No Rotary 590-610

Af. Lease Yes No Rotary 600 3-5

VR No. 8 No No Rotary 600 10
VR No. 9 No No Rotary 400 10

WDL No. 1 Yes Yes Rintoul

WDL No. 3 Yes Yes Rintoul 650 30

Table 7.7 Carbon regeneration at various carbon-based plants

(after Davidson and Schoeman, 1991)

7.32
RECOVERY OF GOLD FROM ELUANTS

Gold can be recovered from eluant solutions by two different

processes:

a) Electrowinning

b) Zinc cementation

The most common procedure is to electrowin the gold onto steel

wool.

ELECTROWINNING

Gold can be recovered from eluants by passing an electric current

through the eluant solution. This process is called electrowinning.

GOLD + ELECTRIC Û GOLD

SOLUTION CURRENT SLIME

Electrowinning is performed in cells, constructed of a non-

conducting material such as fibreglass or plastic that contain the
anode and cathode assemblages. Various types of electrowinning
cells are used including the Zadra, Mintek, AARL and NIM cells.

In the Zadra Cell, the gold collects on the negative electrode or

cathode that is usually a cylindrical polypropylene basket filled
with steel wool. This produces a high surface area for reaction and
increases the speed of the electrowinning process. The positive
electrode or anode does not collect gold but is necessary for the
current to flow. It is usually made of stainless steel. A Zadra cell
will typically draw 150 Amps at 3-4 Volts and exhibit current
efficiencies of 5-10% (Kyle 1987).

In the Mintek cell, cathodes consist of mild steel wool packed into
rectangular polypropylene baskets. The best steel wool loading is
about 5-15g per litre. These fit snugly into a rectangular tank to
prevent liquid bypass. The anode is usually stainless steel mesh.

Typically, a Mintek cell of volume 1 cubic metre can produce 20kg

of gold per 24 hour period with a loading of 15kg gold per kg of
steel wool. Steel wool cathodes can be loaded up to 20 times their
weight with gold but this is rarely done as efficiency decreases as
the gold coating gets thicker. The cell requires about 300-800
Amps at up to 10 volts at current efficiencies of 5-10% (Kyle
1987).

In general, electrowinning efficiency depends on the eluant

concentration. Hence efficiencies increase in the order Zadra ®
Anglo ® Micron. For Micron eluants, aluminium foil cathodes
(plain or shredded) are often used. These produce a higher barren
eluant that is returned to the carbon adsorption circuit. Expanded
aluminium, however, produces a very low barren eluant that can be
rejected.

7.33
ZINC CEMENTATION

Zinc cementation or precipitation can be used as an alternative to

electrowinning for the recovery of gold from eluants. Zinc dust is
added to the gold eluant. The zinc dust dissolves and the gold
precipitates out of solution.

ZINC + GOLD Û GOLD + ZINC

DUST SOLUTION SLIME SOLUTION

Eluants from AARL elution circuits are usually suitable for zinc
cementation. Eluants for Zadra elution circuits however contain
higher concentrations of caustic soda and may be at a higher
temperature. Zadra eluants need to be cooled and diluted before
zinc cementation.

7.34
GOLD PURIFICATION

The gold produced by electrowinning contains iron (steel wool) and

that produced by zinc cementation contains excess zinc. These
impurities must be removed before the gold can be refined. There
are four common purification processes in use.

ACID DIGESTION / SMELTING

This method can be used with the product from both zinc
cementation and electrowinning. The impurity, zinc or iron, is
dissolved with a weak solution of acid at temperatures up to 60°C
for 12 to 24 hours.

ZINC HYDROCHLORIC ZINC OR IRON HYDROGEN

or + Û +
IRON ACID SOLUTION GAS

Some of the iron or zinc may be completely coated with a coherent

layer of gold that prevents the acid from reaching and dissolving
the impurity. The gold filtered and refined further by smelting.

In smelting, the gold slime is melted in a pot with a flux of silica

(SiO2) borax (Na2B4O7), soda ash (Na2CO3) and nitre (KNO3). The
furnace, which operates at over 1200°C, produces molten gold
(M.Pt. 1063°C) and silver (M.Pt. 961°C) and a slag that contains
most of the other metals that were in the gold (copper, zinc, nickel,
iron etc).

The slag is poured first and then the molten gold is poured into a
series of moulds and allowed to cool to produce gold bars.

CALCINING / SMELTING

The steel wool cathodes that have been plated with gold are placed
in trays and calcined at about 750°C for up to 12 hours. A good
flow of air is maintained to oxidise iron and any other base metals.

DIRECT SMELTING

The fluxes used in smelting can be adjusted such that the gold
plated steel wool cathodes can be directly smelted without any
pretreatment. The use of the oxidising agent, nitre, in direct
smelting requires care as excess will oxidise silver and this may be
lost to the slag phase. Gold losses may also be increased by direct
smelting.

ELECTRO-REFINING

A recent innovation involves electrowinning the gold onto stainless

steel wool instead of mild steel wool as is usually the case. The
gold coated cathodes are then loaded into a second cell where they
act as the anodes. Flat stainless steal plate forms the new cathode.

7.35
A fresh sodium hydroxide / sodium cyanide solution is put in the
cell and a current applied. The impure gold dissolves and a purer
produce is plated out on the cathode.

The advantages (Kyle 1987) of this method of gold purification are:

(i) the steel wool can be used many times.

(ii) the gold can be scraped off the plates clearly and
quickly.
(iii) operating costs are reduced.
(iv) a refinery ready product is produced without smelting.
(v) if smelting is done, less slag is produced meaning less
gold is lost in the slag.

7.36
REFERENCES

Adams, M.D. and Nicol, M.J., 1986. The kinetics of the elution of
gold from activated carbon. GOLD 100. Proceedings of the
international conference on gold. Volume 2: Extractive metallurgy
of gold. Johannesburg, SAIMM.

American Cyanamid Company, 1968. Chemistry of cyanidation.

Mineral Dressing Notes, Number 23. American Cyanamid
Company, Wayne, N.J.

Bockris, J.C., 1969. In Chemistry and physics of carbon. vol.5

Walker, P.,C. (ed). New York, Marcel Dekker.

Davidson, R.J. and Schoeman, N., 1991. The management of carbon

in a high-tonnage CIP operation. J. S. Afr. Inst. Min. Metall., vol.
91, no.6. Jun. 1991. 195-208.

Fleming, C.A., 1992. Hydrometallurgy of precious metals recovery.

Hydrometallurgy, 30 127-162.

Fornwalt, H.J., Helbig, W.A. and Scheffer, G.H., 1963. Activated

carbon for liquid-phase adsorption. Br. Chem. Eng., vol 8. 546-

Kyle, J.H., 1987 Chemistry of the CIP process. Gold Plant Operators
Course, Western Australian School of Mines. Department of
Minerals Engineering and Extractive Metallurgy. Kalgoorlie,
Western Australia.

Mattson, J.S. and Mark, H.B., 1971. Activated carbon. New York,
Marcel Dekker.

McDougall, G.J., 1991. The physical nature and manufacture of

activated carbon. J. S. Afr. Inst. Min. Metall., vol. 91, no.4. Apr.
1991. 109-120.

Nicol M.J., Flemming C.A. and Paul R.L. 1987. The chemistry of
the extraction of gold. in Stanley G.G. (Ed). The extractive
metallurgy of gold in South Africa. Vol2, Johannesberg, SAIMM
831-905.

Verhoeven, P., Hefter, G. and May, P.M., 1990. Dissociation

constants of hydrogen cyanide in saline solutions. Minerals &
Metallurgical Processing, November 1990 185-188.

7.37
Van Vliet, B.M., 1991. The regeneration of activated carbon. J. S.
Afr. Inst. Min. Metall., vol. 91, no.5. May. 1991. 159-167.

Yehaskel, A., (ed.). 1978. Activated carbon - manufacture and

regeneration. Park Ridge (USA), Noyes Data Corporation.

7.38