You are on page 1of 34

Universidade de So Paulo,

Escola Politcnica, Dept Engenharia de Minas


PMI 5003

Studying Gold Ores:


Mineralogy, Cyanidation, Toxicity
and Environmental Issues

Gold Process Mineralogy

Dr. Arthur Pinto Chaves


(Universidade de So Paulo, Dept Engenharia de Minas)

Dr. Marcello Veiga


(University of Britsh Columbia, Dept Mining Engineering, Canada)

Common Gold Minerals


Gold
Electrum
Cuproauride
Porpezite
Rhodite
Iridic gold

Au
(Au,Ag)
(Au,Cu)
(Au,Pd)
(Au,Rh)
(Au,Ir)

Calaverite
Krennerite
Montbrayite
Petzite (antamokite)

AuTe 2
(Au,Ag)Te 2
(Au,Sb)2Te 3
Ag3 AuTe 2

Uytenbogaardtite

Ag3AuS2

Aurostibite

AuSb2

Fischesserite

Ag3AuSe2

Common Gold Minerals

Physical Properties of Gold


Property
% Au
SG
Mohs Hardness

Native Gold

Electrum

>75

45-75

16-19.3

13-16

2.5-3

2-2.5

Platinum gold
Bismuthian gold
Gold amalgam
Maldonite
Auricupride
Palladium Curoauride

(Au,Pt)
(Au,Bi)
Au 2 Hg 3 (?)
Au 2 Bi
AuCu3
(Cu,Pd)3 Au 2

Muthmannite
Sylvanite
Kostovite
Nagyagite

(Ag,Au)Te
(Au,Ag)Te 4
AuCuTe 4
Pb 5 Au(Te,Sb)4 S5-8

Physical Properties of Gold Tellurides


Mineral

%Au

SG

Hardness

Calaverite

39.2-42.8

9.2

2.5-3

Krennerite

30.7-43.9

8.6

2.5

Sylvanite

24.2-29.9

8.2

1.5-2

Montbroyite

2.5

38.6-44.3

9.9

Petzite

19-25.2

9.1

2.5

Hessite

4.7

8.4

2.5-3

Physical Properties of Gold Minerals


Au%

SG

Mohs
Hardness

Nagyagite

7.4-10.2

4.5

1.5

Kostovite

25.2

Mineral

2-2.5

Aurostibnite

43.5-50.9

9.9

Maldonite

64.5-65.1

15.5

1.5-2

Gold Mineral Associations and Size


Gold occurs in several forms
Free gold is liberated
Attached to gangue along
grain boundaries or
completely occluded
within a particle grain
Finely disseminated within
a mineral structure.

GOLD

GANGUE

HENLEY, K.J,(1975). Gold-ore mineralogy and its relation to metallurgical treatment.


Minerals Sci. Engng, vol.7, n. 4, p. 289-312

Gold in the Electron Microscope

History of Gold Ore Processing


1700 to early 1900s
Mostly alluvial gold
Gold pans, sluice boxes and mercury amalgamation

Late 1800s to mid 1900s

Cyanidation Invented
Depletion of alluvial gold
Increase in hardrock gold mining
Processing evolved towards cyanidation, although mercury still used in
some large scale operations

1970s to present

Image of back-scattered electrons

Process Design for


Large Scale Gold Mines
Process designs are based on ore specific
mineralogy
Processes are kept as simple as possible
with minimum number of stages
Usually coarse gold is removed first from
the leaching circuit
Cyanidation is usually applied for gold
particles finer than 0.15 mm (100 mesh)

Development of heap cyanidation


New technologies for refractory gold ores
Mercury use in large scale mines almost completely disappears
Centrifugal gravity concentrators developed
Escalation of ASM in developing countries

Typical Terminology for Gold Ores


Alluvial (usually free naturally gold)
 sands and gravels, rivers, beaches
 usually gold particles are liberated
Free milling
 surface and underground hard rock
minesEgold associated with silicates
Refractory
 not amenable to conventional cyanidation
 usually associated with sulfides

Gold Ore Processing Practices


(Alluvial)
USUALLY gold is liberated in
alluvial ore, but sometimes it is not

Gold Ore Processing Practices


(Alluvial)

Scrubbing

Sometimes gold is aggregated


with clayEscrubbing is needed
In Coluvial and Eluvial ores, gold
IS PARTIALLY liberated and this is
the reason why the Au recovery is
low, as many miners do not grind
the ore before concentration

Gravity and/or Flotation


Concentration

Free gold

Gold Ore Processing Practices


(Alluvial)

Brazil, 1993 (BBC Documentary)


Dredging alluvial gold in the Amazon

Gold Ore Processing Practices


(free milling ores)
Comminution

Cyanide
Leach

Comminution

Gravity and/or Flotation


Concentration

Gold

Comminution

Gravity
Sep

Free gold

Flotation

Oxidation

Cyanide
Leach

Free gold

Cyanide
Leach

Gold

Concentration of alluvial gold by flotation. Photo H. Wotruba

Gold Ore Processing Practices


(refractory)

Brazil, 2006
Mining coluvial gold ore
in the Amazon

Typical Terminology for Gold Ores


Attached (occluded) gold
sulfides
Silicates
Invisible gold
Au grains sizes range from:
very coarse >1 mm
coarse >0.15 mm
fine <0.074 mm
to very fine <0.010 mm

25 m

Reflected light in optical microscope


Fine gold in pyrite grain

Gold

Free Gold Particle

Gold Associated with sulfides


Gold rarely forms solid solution with sulfides
but it is possible
Gold can be occluded in sulfides in grains
<0.02 m
Invisible Au can be sub microscopic gold or
gold in the sulfide lattice
Invisible Au is preferentially concentrated in
arsenopyrite which is apparently related to
crystal chemistry
When an ore has fine and coarse grained
arsenopyrite, Au concentrates in finer grained

25 m

Gold Associated with sulfides


Reflected light in optical microscope

Gold Associated with sulfides


Polished-thin Section, reflected light, optical microscope

Ga

Chalcopyrite
CuFeS2

Au

Si

Gold with Galena and Silicates

Gold is usually difficult to polish


(lots of scratches)

Reflected light

Very often in the optical microscope, chalcopyrite looks like


gold, but gold is much brighter
HENLEY, K.J,(1975). Gold-ore mineralogy and its relation to metallurgical treatment.
Minerals Sci. Engng, vol.7, n. 4, p. 289-312

Gold Associated with sulfides

Gold Associated with Sulfides


To differentiate Au from Chalcopyrite
Reflected Light

Reflected Light

gold

gold
chalcopyrite

gold

sulfides (chalcopyrite and pyrite) become oxidized in


the optical microscope when the specimen is attacked
by diluted HNO3 (10%) for one day

Studying of Liberation of Gold Ores

increasing liberation.

Grain size distribution


of a garimpo tailing
before grinding.

Au 1.5
(g/t) 1
0.5

Grain size
analyses

conc.
Fire Assay

It is noticeable that
the Artisanal Miners
could not recover the
fine gold (they used
sluice boxes) and the
unliberated gold in
the coarse fractions.

#
10
0#
15
0#
20
0#
27
0#
40
0#
-4
00
#

65

25

Au 20
15
distr.10
(%) 5
0

65
#
10
0#
15
0#
20
0#
27
0#
40
0#
-4
00
#

tail.

Mesh

Gold grades in screened fractions

- 20 min.
- 30 min.

Batch
Flotation

28

20

Grinding
(various time)

- no grinding
- 5 min.
- 10 min.

28
#

grinding time

20
#

Composite
Sample

The average gold grade of this tailing from Crixs, Brazil is


around 0.7 to 1 g/tonne. Gold liberation was studied as follows::

3
2.5

48
#

Increasing grinding time

Example

35
#

Studying Liberation by Flotation or Gravity Concentration

48

Studying Liberation by Flotation or Gravity Concentration

35

Studying Gold Liberation

It is difficult to establish gold liberation as


this is usually a trace element in most
ores, hardly visible in microscope.
Liberation of gold can be obtained by
indirect methods, such as heavy liquid
separation, gravity concentration,
flotation, etc..
One technique (very common) to
establish the gold liberation is grinding in
different times followed by concentration

Mesh
Gold distribution in screened fractions

Studying Liberation by Flotation or Gravity Concentration

Studying Liberation by Flotation or Gravity Concentration

Concentration of the different ground sub-samples indicates


that the liberation must be around 10 minutes of grinding.
Taking this information to the grain size distribution graphic,
we can obtain the liberation size of the gold particles.
% Mass Passing

100

100
90

%Gold
recovery
80
by
concentration 70

80
grinding time

60
40

1 min
5 min
10 min

20

20 min

D80 for 10 min of grinding


(probable gold liberation)

0
16

60

20

28

35

48

65

100

150

200

270

400

-400

Tyler Mesh

50
0

10

20

30

Grinding time (min.)

Studying of Liberation of Gold Ores

Very often the concept of gold liberation


is usually replaced by accessibility of
gold to reagents such as mercury,
cyanide, etc.
In other words: submit the sample (or
concentrates) to cyanidation and
amalgamation.
The grain size distribution must be
knownE.or make cyanidiation or
amalgamation of the sized fractions

Studying of Liberation of Gold Ores

Au exposed but not liberated


Quartz particle

Hg Activation Improves Amalgamation

Hg Activation Improves Amalgamation


Usually Hg becomes oxidized (dirty) when
it is old
The efficiency of amalgamation is low
(usually 70%)EHg doesnt grab Aut
Hg forms droplets and loses coalescence
Lots of Hg is lost to amalgamation tailings
(usually have 60-300 ppm Hg)

For amalgamation a gold particle must


be at least >90% liberated
Amalgamation is difficult for -200 mesh
fractions unless the mercury is activated
For cyanidation gold does not need to be
liberated; it can be exposed

Boil water (Indonesia)


Detergent (Brazil, Zimbabwe, Tanzania)
Lime juice (Laos)
Dilluted nitric acid (Peru)
Brown sugar (Ecuador)
Molasse, guava leaves, lime juice, bicarbonate
(Colombia, Antioquia)
Urine (Chile)
Electrolytic formation of Na- or K-amalgam
(Colombia, Narios)

Activating Hg before amalgamation


(increase coalescence = reduces Hg
flouring = less Hg loss with tailing)

+
wire

Battery
12 V

It forms sodiumamalgam which is


more consistent
than pure Hg

Graphite rod

Mercury

Water with 10%


of salt NaCl or
KCl

Brazil, 2006

Zimbabwe, 2006

Brown Sugar in the Amalgamation Barrel

Amalgamation Barrel

Ecuador, 2004

It is not know the role of brown sugar in improving


amalgamtion. This is widely used in Ecuador and some
parys of Colombia

Indonesia, 2006

Studying of Liberation of Gold Ores

Studying of Liberation of Gold Ores

A Simple Methodology: screened fractions


are submitted to heavy liquid separation.
The floats are assayed for gold. The sinks are
submitted to amalgamation. The mineral
residue is submitted to cyanidation.
This will determine the gold portion accessible
to mercury (almost free gold) and accessible to
cyanide (not quite free).
The final residue, after cyanidation is analyzed
by fire assay, in which all ore is melted. This
determines the portion of mineral-locked gold
(not amalgamated or leached).

ATTENTION:

This is just a lab test


This must not be used in an actual
processing plant
Hg-contaminated tailings must not be
leached with cyanide since this forms
Hg-cyanide which is very bioavailable

Studying of Liberation of Gold Ores

Studying of Liberation of Gold Ores

Gold Ore (8g/tonne Au)

Results:

35, 48, 65, 100, 150, 200, 270


mesh

Screening

light fractions
Heavy Liquid
Separation
heavy fractions
amalgams
Amalgamation

(60% solids; Hg:solids = 1:20)

residue
Cyanidation
(*)
(*)

(10g/L NaCN,
NaCN, pH=10, 40%sol, 24 h)

All fractions finer than 48 mesh had similar Au recovery (~60%) in


heavy liquid. Amalgamation showed that particles coarser than 48
mesh did not show enough exposure to be amalgamated.

Crushing ((-28#)

solutions

Chemical Analysis
Nitric Acid
Hg--Dissolution
Hg

gold

Chemical
Analysis

gold

residue
Fire Assay

Fraction
(Tyler mesh)
-28 +35
-35 +48
-48 +65
-65 +100
-100 +150
-150 +200
-200 +270

(*)

gold

Just the -48 mesh fractions were leached


by cyanide. High concentration of CN was
used to avoid CN consumpion control

Gold in Heavy
Products (%)
32
68
57
55
62
60
n.a.

Amalgamated
Gold (%)
4
1
21
48
67
87
n.a

CN Leached
Gold (%)
n.a
n.a
n.a
88.0
93.2
95.0
99.0

We should expect to extract up to 60% of the gold from this ore


ground -65 mesh and subjected to gravity separation.
Cyanidation of -200 mesh recovers almost all gold.

Studying of Liberation of Gold Ores

Studying of Liberation of Gold Ores

Example:
Gold liberation of an ore from Texada Island, BC, Canada As the ore had more
than 30% of heavy minerals (pyrite, bornite, iron oxides) (sg>2.89) and high
gold grade (7.3 g/t), the heavy liquid separation was not used, just
amalgamation followed by cyanidation and fire-assay (fusion) of final residues.
It is possible to notice the gold liberation increasing with particle size
decreasing.

Representative
sample

Store in bags

Fusion

75

Cyanidation

50

- +100#

- 6 Mesh (3.4 mm)


sub-samples

sub-sample

(polished thin sections)

Crushing

DAu (%)
100

25

Optical and electron


microscopy

Chips of sample
selected

Amalgamation
-200+400#
-400#
-100+200#

Grinding
- 28 M (0.6 mm)
Screening
fractions
Heavy Liquid
Separation
heavies

Liberation of Sulfides
(Microscopy)
Chemical
Analysis

Gravity Sep.
tailing
Flotation
conc.
Cyanidation
residue
Diagnosis
Leaching

Amalgamation
residues

Overall Gold recovered by:

Cyanidation

Fusion:
Cyanidation:
Amalgamation:

11.4 %
64.0 %
24.6 %

residues
Fire Assay

Studying of Liberation of Gold Ores

Clifton et al. (1969) calculated the size of sample required to contain 20


particles of gold (spheres) as a function of gold particles and grade,
assuming that Au particles are uniform and randomly distributed.
Size of Gold
Particle (mm)

The mass of sample to


be used is a function of
the gold particle shape,
size and distribution.

= splitting
= optional

Studying of Liberation of Gold Ores

Grinding with
different times

kg of sample required
4 ppm Au

1 ppm Au

2.0

400

1000

1.0

50

200
30

0.5

0.25

0.125

0.1

0.5

0.062

0.02

0.05

0.031

0.002

0.006

0.015

0.0002

0.002

0.008

0.00002

0.0001

According to Clifton et al. (1969) a precision of 50% is


achieved at 95% certainty when a sample for analysis
contains a minimum of 20 gold particles
Usually 100 kg of a representative sample crushed below
1/4" (6.35 mm) is a good starting material.
If gold particles are not larger than 0.25 mm (no nuggets),
material can be stored in 1 kg bags after crushed below 6
Mesh (3.4 mm).
When there is indication of presence of >1mm nuggets the
entire process becomes complex as we cannot work with
small samples.
When the amount of sulfides in the ore is low (<2%) it is
convenient to concentrate the screened fractions in heavy
liquids before the microscopy (Gaudin Method)

History of Gold Cyanidation


Date

Name

Discovery

6th
Century

Jabir
Hayyan

Discovered aqua regia & that it dissolved gold


6HCl + 2HNO3 + 2Au 2AuCl3 + 2NO + 4H2O

1704

Gold Cyanidation

Discovered Prussian Blue (Fe4[Fe(CN)6]3) by


accidentally combining dried blood with potash
(K2CO3) and treating with iron vitriol (FeSO4)

1774

C.W.
Schule

Discovered chlorine & that it dissolved gold

1852

K.F.
Plattner

Applied chlorination to gold recovery


2Au + 3Cl2 2AuCl3

Early
1700s

P.J.
Discovered potassium ferrocyanide
Macquer (K4[Fe(CN)6]) by combining Prussian Blue with
Alkali (KOH)

1782

C.W.
Schule

Discovered Blue Acid by heating Prussian Blue


with Dilute Sulphuric Acid

Date

Name

1811

J.L. GayLussac

1834

Potassium cyanide produced by fusing potassium


ferro cyanide with potash K4[Fe(CN)6] + K2CO3
6KCN + FeCO3

1. Oxygen Theory, L. Elsner (1846)


2. Hydrogen Theory, L. Janin (1888)

1840

Elkington

Patented process using KCN to prepare


electrolyte for electroplating Au and Ag

1846

L. Elsner

Recognized importance of oxygen to dissolution of


Au with cyanide
4Au + 8KCN + O2 + 2H2O 4KAu(CN)2 + 4KOH

1887

Cyanidation Process (theories)

Discovery
Determined Blue Acid was HCN

J.S.
MacArthur,
R.W.
Forrest,
W. Forrest

4Au + 8NaCN + O2 + 2H2O 4NaAu(CN)2 + 4NaOH


2Au + 4NaCN + 2H2O 2NaAu(CN)2 + 2NaOH + H2

3. Hydrogen Peroxide Theory, G. Bodlander (1896)


2Au + 4NaCN + O2 + 2H2O 2NaAu(CN)2 + 2NaOH + H2O2
H2O2 + 2Au + 4NaCN 2NaAu(CN)2 + 2NaOH
4Au + 8NaCN + O2 + 2H2O 4NaAu(CN)2 4NaOH

Patented process for dissolution of Au from ore


using weak cyanide solution and to precipitate Au
with zinc shavings. Process was considered a
significant improvement over amalgamation and
chlorination.

Cyanidation Process (theories)


4. Cyanogen Formation, S.B. Christy (1896)
O2 + 4NaCN + 2H2O 2(CN)2 + 4NaOH

5. Corrosion Theory, B. Boonstra (1943)


O2 + 2H2O + 2e H2O2 + 2OHAu Au+ + e
Au+ + CN- AuCN
AuCN + CN- Au(CN)2
Au + O2 + 2CN- + 2H2O + e- Au(CN)2- + 2OH- + H2O2

Factors Affecting Cyanidation

Hedley and Tabachnick (1968) listed the main factors


affecting cyanidation:
 dissolved oxygen
 pH
 stability of cyanide solutions
 cyanide concentration
 gold particle size and shape
 accessibility of cyanide to gold (exposure)
 silver content (silver dissolves slower than gold)
 temperature
 presence of minerals consuming oxygen
 presence of cyanicides
Hedley, N. and Tabachnick, H., 1968. Chemistry of Cyanidation. Mineral Dressing Notes, n. 23.
American Cyanamid Co.
Veiga, M.M. and Klein, B. (2005). Cyanide in Mining. Edumine.com.

Cyanide Stability

pH of Gold Cyanidation

bitter
almond
smell

Au Dissolution Rate

CN- + H2O = HCN + OHNaOH


Ca(OH)2
10.5

pH
Au cyanidation is more efficient at pH=10.5
Ca(OH)2 precipitates on gold surface inhibiting the cyanide
attackE.avoid high pHs

Oxygen in Cyanidation

Cyanidation Process
Mechanisms
Oxygen adsorption into solution
Transport of dissolved O2 and CN- to S/L
interface
Adsorption of O2 and CN- onto gold surface
Electrochemical reaction
Desorption of soluble Au-CN complexes (e.g.
Au(CN)2-) and other reaction products from
solid surface
Transport of soluble products into solution

Normal Cyanidation
In normal conditions of cyanidation, the minimum NaCN
concentration to extract gold is 75 mg/L.

The level of dissolved oxygen controls the kinetics of


gold cyanidation
The concentration of cyanide does not usually determine
the rate of the gold cyanidation reaction
The level of dissolved oxygen required for the
cyanidation process depends on the cyanidation
reactions and cyanide consumption by other substances
(cyanicides).
The concentration of dissolved oxygen also depends on:
- pressure (altitude)
- temperature
- agitation
- ionic strength of the solution

Silver Slows Down Cyanidation

4 Au + 8 NaCN + O2 + 2 H2O = 4 Na[Au(CN)2] + 4 NaOH


Gold cyanidation employs diluted sodium or potassium
cyanide solutions containing 100 to 1000 mg/L.
In average 100 tonnes of NaCN are needed to extract 1
tonne of gold
Most plants operate at between pH 9.5 and 11.5.
Cyanide consumption usually is between 0.05 and 5 kg
NaCN/tonne of oreE.for cyanidation of concentrates, the
cyanide consumption can be higher (>5 kg/t)

Some Minerals Consume Cyanide

Some of the cations that form stable


complexes with cyanide, and in the process
consume cyanide, are: Cu+, Cu2+, Fe2+, Fe3+,
Mn2+, Ni2+, Zn2+.
One way to eliminate the cyanide consumption
problem is to remove cyanicide, e.g. pyrrhotite,
by magnetic separation or flotation (assuming
it does not contain a significant amount of
associated gold) prior to cyanidation.
Other methods include adding lead nitrate, or
oxidation of the sulfides by pre-aeration,
oxygen or peroxide.

Effect of Lead Nitrate

Lead nitrate reduces cyanide consumption and


speed up the gold leaching reaction
Pb forms insoluble PbS removing passivation
ions (S2+) from gold surface
Local galvanic cells between is also formed on
gold surface
In a cyanide solution, lead nitrate, lead sulfide
and lead sulphite react with gold to form
AuPb2, AuPb3 and metallic lead, which clearly
accelerate the gold dissolution

Deschenes et al (2000/ Minerals Engineering v.13, n.12, p.1263-1279.

10

Effect of Lead Nitrate

Some Minerals Consume Cyanide

Au Extraction (%)

50 g/t Pb(NO3)2

No Pb(NO3)2

Time (h)

Ore: 4.2 g/t Au, 0.9 g/t Ag, 3.1 pyrrhotite, 0.4% pyrite,
Conditions: 0.38 g/L NaCN, pH 10
Deschenes et al (2000/ Minerals Engineering v.13, n.12, p.1263-1279.

Some Minerals Consume Cyanide

Some Minerals Consume Cyanide

Pyrrhotites range from Fe5S6 to Fe16S17

Some Minerals Consume Cyanide

Some Minerals Consume Cyanide

When high concentrations of cyanideconsuming minerals (in particular Cu minerals)


exist in a ore, cyanidation may become
uneconomical as this results in poor gold
recovery and high operating costs
The ammonia-cyanide leaching system is an
alternative approach. It is proposed that the
ammonia stabilizes a copper(II)-ammoniacyanide complex such as Cu(NH3)4(CN)2 that is
responsible for gold dissolution

11

Preg-Robbing Ore

Preg-Robbing Ore

Gold in solution can also be adsorbed by some


mineralogical components of the ore.
These are known as 'preg-robbing'
substances.
The most common preg-robbing substances
are carbonaceous materials which are organic
substances with high surface area.
Not all carbonaceous material is activated

One way to eliminate this effect, in milder


cases, is addition of diesel or kerosene to the
leach to deactivate the carbonaceous matter,
This has to be done with caution otherwise the
posterior carbon-in-pulp (CIP) process
(adsorption of gold on activated charcoal) could
be adversely affected.
The addition of kerosene can effectively
passivate the carbonaceous material by coating
it. This process is suitable for ore with less than
1% carbonaceous material.

Preg-Robbing Ore

Preg-Robbing
Ore

In other circumstances, the organic matter must


be eliminated prior to cyanidation by flotation or
by oxidization / burning
Most common procedure to overcome this
effect is the CIL (carbon-in-leach) process.
AC is introduced into the leaching process and
soluble gold is immediately adsorbed by the
charcoal.
The process takes advantage of the fact that
the adsorption kinetics of gold on charcoal is
faster than it is on the preg-robbing
mineralogical species

Recovering Gold from Cyanide Solutions


Gold can be recovered from CN solution by 3 methods:
 Activated Charcoal (AC) Adsorption
 Zinc precipitation (Merrill-Crowe

Adsorption with Activated Charcoal (AC)


 Carbon-in-Pulp (CIP)
 Carbon-in-Leach (CIL)
 Carbon-in-Columns (CIC)

Recovering Gold with Activated Charcoal


Ore or Conc.

Ore or Conc.

Ore or Conc.

Cyanidation

Cyanidation
with AC

Cyanidation

pulp

CIP

AC

Separation S/L

AC

Elution
Au rich solution

solution

Elution

solution

 Resin Adsorption
The first two are the most popular methods

Source: Marsden, J.O, House I.


2006. The chemistry of gold
extraction. 2nd ed. Littleton, CO:
SME Society for Mining,
Metallurgy and Exploration. 651p

Columns with AC

Au rich solution

AC

Electrolysis

Electrolysis

Elution

Gold

Gold

Electrolysis

Au rich solution

Gold
AC = activated chacoal

12

Recovering Gold with Activated Charcoal

Activated Charcoal (AC) Properties:


- Adsorptive Capacity (porous)
- Adsorption Rate
- Mechanical Strength and Wear Resistance
- Reactivation Characteristics
- Coarse Grain Size

Most AC are manufactured from coconut shell

Other materials can also be used anthracite, peat, etc.

Recovering Gold with Activated Charcoal

Recovering Gold with Activated Charcoal


The CIP method (Carbon-in-Pulp ) makes use of the
physical affinity that activated charcoal (AC) has for gold
(it can attract 7% of its weight in gold), which it readily
attracts to its surface in cyanide solution.
Usually the industry does not load the AC with more than
8000 g Au/t charcoal = 0.8%
The following figure shows that less gold stays in
solution when the max load is 5000 ppm
Adsorption rate on AC is rapid initially as Au adsorbs to
most accessible sites but then decreases as rate
controlled by diffusion along pores.

Recovering the AC
As the particles of AC are
coarser than the ground ore,
the AC is screened after the
cyanidation
The fine material is sent to
cyanide destruction
Some fine AC particles (with
Au) can be lost if the charcoal
does not have good physical
properties
Ecuador, 2009

Source: Marsden, J.O, House I. 2006. The chemistry of gold extraction. 2nd ed. Littleton, CO: SME Society for Mining,
Metallurgy and Exploration. 651p

Elution of Activated Charcoal


After loading the AC, gold must be extracted
(eluted) from the charcoal surface
Elution procedures are very variable. Just a high pH
solution can strip Au from the AC, but this takes
time.
Usually companies use a cyanide solution 1-2 g/L
and 10 g/L of NaOH and temperature 90-100 oC
and up to 72 hours to strip >97% gold from AC
Elution is not done everyday. Wait for the charcoal
to be loaded (5000 8000 gAu/t AC)

Elution of Activated Charcoal


Solvents such as ethanol (10 to 20% vol) can
speed up the process to be completed in 8
hours
The elution solution, now with 1000 to 3000 mg
Au/L (ppm) is submitted to electrolysis
Some people use Zn to precipitate Au from the
elution solution
Excess zinc is dissolved with acid, and gold is
melted

13

Elution - Stripping of Au from AC

Recovering Gold with Activated Charcoal


Figure: the elution solution
(7 m3) is heated in a diesel
oil burning column and
pumped through two
columns filled with the
loaded activated charcoal
Stainless steel columns
work in series to the
electrolysis cell and then to
a large holding tank,
insulated with Styrofoam in
a wooden box which in turn
feeds the heating vessel.

Recovering Gold with Activated Charcoal


After elution, the AC must be treated with nitric or
hydrochloric acid to remove contaminants.
Usually the charcoal is treated after 10 to 12 times of use
After acid treatment, the AC is heat to 500 C.
Impurities are removed as gases or remain as a tar-like
residue.
Then the charcoal is exposed to an oxidizing
atmosphere of steam containing CO2 and O2 at 700
1000 C. This burns off the tar-like residue, develops
internal pore structure, and the carbon atoms at the
edges of crystallites become 'active sites' due to
unsaturated valencies.

Typical Carbon-in-Pulp Process Flowsheet


Ore or Conc.
Re-cycle to Process
Comminution
Cyanide Leach
pulp

CIP

Recovering Gold with Zinc

4Au + 8CN- + O2 + 2H2O = 4Au(CN)2- + 4OH2Au(CN)2- + Zn = Zn(CN)42- + 2Au (Merrill-Crowe process)


Pulp is filtered and the clarified solution is then passed
through a vacuum de-aeration tower where oxygen is
removed from the solution.
Zinc powder is added to the solution with a dry chemical
feeder. The reaction of the special fine powder zinc with
the solution is almost instantaneous. Precipitated gold is
recovered by filtering.

Cyanide Destruction

solution

AC

Tailings Pond

Elution
Electrolysis
Gold

The Merrill-Crowe process is usually preferred over the


charcoal process when the pregnant solution is high in
Ag, or other metals like Hg, as these metals very quickly
plug the pores of the charcoal

Elution columns in Portovelo, Ecuador

solution

In the case of leaching concentrates,


comminution is not always needed

Merrill-Crowe Process
(Factors Affecting Zinc Precipitation)
Suspended solids - interfere with the process possibly
by coating the Zn particles and contaminate the final
concentrate. Therefore, leach slurries are filtered to
remove solids prior to Zn precipitation.
Dissolved Oxygen - oxygen reduction competes with
Au reductions, therefore, dissolved oxygen reduces
precipitation kinetics. De-aeration is required to lower
dissolved oxygen levels to <0.5 - 1.0 mg/l prior to
precipitation.
pH - the process is not very sensitive over pH range of
9 to 12. Above and below this range, precipitation
decreases

14

Merrill-Crowe Process
(Factors Affecting Zinc Precipitation)

Typical Merrill-Crowe Process Flowsheet


Ore or Conc.

Cyanide concentration - minimum concentration


required otherwise rate of precipitation is reduced
(Typically > 0.05 - 0.20 g/L)
solution

Temperature - precipitation kinetics are accelerated at


elevated temperatures
Gold concentration - precipitation rate increases with Au
grade of solution
Zinc concentration - at high Zn concentrations, the
dissolution rate of Zn can be slow. Also, high Zn
concentrations can lead to formation of insoluble Znhydroxide which passivates Zn surface. Zn added at 5 to
30 times the stoichiometric Au requirement.

Re-cycle to Process

Comminution
Cyanide Leach
pulp

pulp

S/L Separation

Settling Tank

pulp

solution

solution

pulp

Precipitation w/ Zn

Cyanide Destruction

Leach with Acid

Tailings Pond

pulp

Precipitate w/Al

Gold

In the case of leaching concentrates,


comminution is not always needed

Zinc

Electrowinning
Instead of Zn precipitation, electrolysis can be used to treat
high-grade gold solutions (carbon eluates) to produce
loaded cathodes or cathode cell sludges

Main Cyanidation Practices


Agitated Tanks
CIP (Carbon-in-Pulp)
CIL (Carbon-in-Leach)

Au(CN)2- + e- Au + 2CN Advantages (over Zn precipitation)

Static leaching

 No chemicals or metals introduced in process


 More selective for Au and Ag over Cu

Vat leaching with Carbon-in-Column or Zinc ppt


Heap leaching with Carbon-in-Column or Zinc ppt

Intensive cyanidation (for concentrates)

Higher purity product


Disadvantages
 Low single pass efficiency per unit cell requiring
recirculation of solution to achieve acceptable extraction

Gekko
Acacia
Mill-leaching (cyanidation in a small ball-mill)

 It needs high Au concentration in solution

Cyanidation in Agitated Tanks in Small-scale


Cyanidation is being used in
160 tanks in Zaruma-Portovelo
region
Tanks range from 10 to 20 m
processing from 4 to 20
tonnes/day
Some plants use either MerrillCrowe or CIP (Carbon-in-Pulp)
techniques

Cyanidation in Agitated Tanks in Small-scale


CIP: 3 tanks = 9 hours, 100 tonnes/d, 2 g Au/t
0.7 g NaCN/L, consumption = 2.5 kg NaCN/t of ore

Ecuador, 2009

Ecuador, 2009

15

Cyanidation in Agitated Tanks in Small-scale


Merrill-Crowe process in Ecuador
The concrete tanks are loaded with 3,600-4,500 kg of sluice
(canalone) concentrate and filled with about 11 m3 of
cyanide solution that ranges from 2 to 4 g NaCN/L.
After 12 hours, agitation is stopped to allow the pulp to
settle. The semi-clarified solution flows by gravity to a
holding tank and then through 4 clusters of 4 PVC columns
containing a total of 11 kg of zinc shavings.
Gold precipitation is not efficient as it is not conducted in
vacuum.
Miners do not leach Zn with acid to obtain gold, they simply
evaporate the zinc (bad practice!!!)

Cyanidation in Agitated Tanks in Small-scale


Merrill-Crowe process in Ecuador

Ecuador, 2007

Cyanidation in Vats

Cyanidation in Agitated Tanks in Small-scale


Merrill-Crowe process in Ecuador

Vat leaching: cyanide solution slowly percolates


through ore in a static tank.
Ore can be coarser than in agitation leaching, with
sizes of <1 cm.
Ore is not agitated and coarse material must have
good permeability.
Very fine grain sizes of <1 mm may tend to block the
free circulation of the leaching agent.
The leaching period is 2 to 4 days and gold recovery
is approximately 70 to 80%.

Ecuador, 2007

Cyanidation in Vats

Some artisanal miners leach for 30 days

Vat-leaching in the Tapajs Region,


Amazon, Brazil
Tailing pond
(baixao)

Vat-leaching
tank

Pool with CN
solution

Artisanal Gold Miners in Zimbabwe using Amalgamation


Tailings to fill the cyanidation vat
Tanks with
activated charcoal

Pool with
pregnant solution

96

16

Heap Leaching

Cyanidation in Heaps
Heap Leaching: the cheapest but slowest technique
of gold cyanidation
It is a process usually applied to low-grade gold ore.
The ore is piled to a given height on an inclined
impermeable surface, a so-called leach pad.
A sprinkler system provides a continuous spray of
alkaline cyanide solution that percolates through the
ore, dissolving the gold.
The gold-bearing or pregnant solution is collected
and pumped to a gold recovery plant.

http://www.sulliden.com/projects/shahuindo-gold-project.aspx

Cyanidation in Heaps
The amount of material contained in a heap can
reach 400 million tonnes (Yanacocha). Leaching time
ranges from several weeks to a few months. Gold
recovery rarely exceeds 70%

Cyanidation in Heaps
Yanacocha Mine, the 4th gold producer in the world.
Location: Cajamarca, Peru, 4700 m above sea level
Started in 1993. In 2005, produced: 3.3 Moz gold
Ore Production: 544,000 tonnes/d @ 0.9 g Au/t
Rock is crushing and agglomerated with cement before
going to the heap. Au recovery = 74%
Waste:Ore Ratio ~0.40
Solution: 0.1 g/L NaCN, pH 10.5, 10 L/h/m2, NaCN
consumption 0.06 kg/t ore

Installing the plastic pads


http://www.mining-technology.com/projects/minera/

Yanacocha Mine, Peru


http://www.mining-technology.com/projects/minera/minera2.html

Au is adsorbed on activated charcoal, and then eluted


solution is precipitated with zinc or submitted to
electrolysis
http://www.geomineinfo.com/Complimentary%20Downloads/Yanacocha.pdf

Intensive Cyanidation

Many mining companies do not concentrate


gold before leaching it with cyanide
The whole ore cyanidation is a common practice
usually when gold is very fine, hard to liberate
but the rock is prorous to allow penetartion of
cyanide solution
The operating cost of whole ore leachingis
higher than cyanidation of concetrates also
called intensive cyanidation
The cost of destroying cyanide is high when the
whole ore is leached

Intensive Cyanidation

Coarse gold takes a long time to be dissolved in


normal cyanidation solutions.
In normal conditions of cyanidation the solubility
rate of pure metallic gold is 3.25 mg/cm2/hour.
Pure silver dissolution rate is 1.54 mg/cm2/hour.
The more silver, the slower is the dissolution of
the Au-Ag alloy
Then a pure gold grain of 44 m (400 mesh)
would take about 13 hours to dissolve.
A 150 micron (100 mesh) diameter pure gold
particle would need almost 44 hours to dissolve.
Hedley, N. and Tabachnick, H., 1968. Chemistry of Cyanidation. Mineral Dressing Notes, n. 23.
American Cyanamid Co.

17

Intensive Cyanidation

In the past many companies used gravity


concentration followed by amalgamation of the
gold in the concentrate.
Amalgamation was used to remove the
coarse (100 m) gold
The tailings from amalgamation was leached
with cyanide.
Problem: this forms mercury cyanide which is
very toxic and also consumes cyanide.
Most organized mining companies no longer
use amalgamationEartisanal miners use 1000
tonnes Hg/annum

Intensive Cyanidation
To leach coarse gold a strong oxidant is needed.
The concentration of the oxidizing agent is more
important than a high cyanide concentration.
High concentration of cyanide is used because, in an
oxidant environment, cyanide will be oxidized as well,
forming cyanate (CNO-).

Intensive Cyanidation

If the ore has coarse gold (>100 m),


companies use gravity concentration and/or
flotation.
They concentrate gold until >3000 g Au/tonne
and melt it with borax.
Problem: gold can be in the slag and this must
be leached with cyanide or all middling
products in the gravity sep. must be recyled
Recently, mining companies are concentrating
gold (gravity or flotation) followed by leaching
the concentrate: Intensive Cyanidation

Intensive Cyanidation
Intensive cyanidation of gravity and flotation
systems have been used by GEKKO and
Acacia Systems
The GEKKO process is a thin film in a drum

5 to 20 g/L of NaCN is used


Use of catalysts Leachwell or LeachAid or hydrogen
peroxide (up to 0.5 g/L) is common
Temperature can also increase cyanidation rate

Intensive Cyanidation

Intensive Cyanidation

Acacia System CS 250: 375 kg conc./cycle

Acacia System:

Knelson Centrifuge
provide concentrates
for the reactor

Pre-washing of the gold concentrate to remove


ultra-fine solids (slimes)
NaOH, NaCN and LeachAid
Agitation for 16 hours with warm CN solution
Decanting and wash the solids with water
Electrowinning
Tailings sent to the normal cyanidation circuit

http://www.knelsongravitysolutions.com/page361.htm
http://www.knelsongravitysolutions.com/page361.htm

18

Intensive Cyanidation

Intensive Cyanidation
A good methodology to investigate intensive
cyanidation of gravity concentrates can be:
Concentrate is ground with different times and
leached with cyanide (5 to 20 g/L) for 1 to 12
hours, 40% solids and pH 10.5 to 11 and
presence of H2O2 (0.3 g/L = 100mL of 3% v.v.
H2O2 solution in 1 L of water)
It is always useful to do CIL Carbon-in-Leach
process to avoid any preg-robbing effect

Veiga,M.M.; Nunes,D.; Klein,B.; Shandro,J.A.; Velasquez,P.C.; Sousa,R.N. (2009). Replacing Mercury Use
in Artisanal Gold Mining: Preliminary Tests of Mill-Leaching. J. Cleaner Production, v.17, p.13731381

Small-scale Intensive Cyanidation implemented


in Tapajs, Brazil
+2mm
Screen 2 mm

Hammer mill

Gold ore

(Mill-leaching)
The ore is not primarily finely ground (this can be
conducted in a hammer-mill)
Gold concentration in centrifuge or in sluice boxes or jig or
flotation
Unliberated gold is also concentrated = pre-concentration
Concentrate is taken to a small batch ball-mill with cyanide
and a capsule of activated charcoal
Leached for 8 hours with 10-20 g/L NaCN and 0.3 g/L
H2O2, pH 10.5.
Remove the capsule of activated charcoal
Elution
Electrolysis or precipitation with zinc and leaching with
acid

A Simple Intensive Cyanidation System


Icon centrifuge: 2 tonnes/h of ore

-2mm
Icon centrifuge
tailing
Icon centrifuge
tailing
flotation

co
nc
.
conc.

.
nc
co

Intensive
Cyanidation
activated
charcoal
elution

final
tailing

electrolisis

meting
gold

Icon (Falcon) centrifuge

A Simple Intensive Cyanidation System


Re-grinding the centrifuge
concentrates

Source: Falcon
website, 2009

Capacity: 2t/h
Pulp: 30% solids
Cycle: 15 to 30 minutes
Bowl: 1kg concent. (dry)
Day: 40 to 80kg conc
Au recovery: 50 to 65%

Capsule of activated
charcoal in the ball mill
Sousa,R.N.; Veiga,M.M.; Klein,B.; Telmer,K.; Gunson,A.J.; Bernaudat,L. (2010). Strategies for Reducing the
Environmental Impact of Reprocessing Mercury-contaminated Tailings in the Artisanal and Small-scale Gold
Mining Sector: Insights from Tapajos River Basin, Brazil. In press by Journal of Cleaner Production.

19

Centrifuge concentrate
[CN] 20 g/L, 0.3 g/L H2O2
grinding

Intensive Cyanidation in Ball Mill


This is an easy procedure
Replace the use of Hg in
these small ball-mills
Capsule of activated
charcoal can be added
together with rods or
ballsEbut this depends
on the resistance of the
capsule
If necessary grind first,
remove rods and add the
AC capsule later

Same but no grinding

Conventional cyanidation
Head sample, [CN] 1g/L,
pH 10-11, no grinding

Ecuador, 2009

Sousa,R.N.; Veiga,M.M.; Klein,B.; Telmer,K.; Gunson,A.J.; Bernaudat,L. (2010). Strategies for Reducing the
Environmental Impact of Reprocessing Mercury-contaminated Tailings in the Artisanal and Small-scale Gold
Mining Sector: Insights from Tapajos River Basin, Brazil. In press by Journal of Cleaner Production.

Intensive Cyanidation Tests in


Ecuador
Concentrate from sluice boxes (17,3 g Au/t)
was split in 3 subsamples:
Amalgamation (160 kg)
Conventional cyanidation in tank (695 kg)
Intensive cyanidation in ball mill (80kg)

Result of Amalgamation
Manual
amalgamation
8 hours in a batea
with mercury and
brown sugar
Gold recovery from
the gravity
concentrate after
amalgamation was:
26%

Ecuador, 2007

Ecuador, 2007

Result of Conventional Cyanidation

Result of Intensive Cyanidation in Ball Mill

In agitated tank
pH = 11
Gold recovery from the gravity concentrate
after 31 horas was: 94%
NaCN consumption was 4.5 kg/t of
concentrate

Gold recovery after


8 hours of millleaching the
concentrate was:
95%
Cyanide
consumption was
0.95 kg/t of
concentrate

Ecuador, 2007

20

Results of Elution of Activated Charcoal

Intensive Cyanidation (conclusion)


For environmental and economic reasons,
intensive cyanidation of gravity and flotation
concentrates must be the future of gold mining
industry.

NaCN = 2g/L, NaOH = 10 g/L


Alcohol = 20%
Temperature: 90 C, 8 h
97% of gold removed from the
activated charcoal
Gold precipitated with small
amount of zinc
Zinc leached with HNO3
Zinc can also be precipitated
with aluminum (cementation)

Coarse gold particles (up to 1 mm) can be


leached in intensive cyanidation circuitsEthe
use of catalysts (oxidants) is fundamental.
This reduces liability and operating costs
Capital costs is not much higher but depends
on flotation and gravity concentration circuits
Ecuador, 2007

Diagnosis Leaching
This is a procedure to assess why the gold is not being
extracted by classical cyanidation (low CN concentration
and no peroxide)

Tests to Check Accessibility of


Cyanide to Gold Particles

First of all, the sample must be ground below 0.1 mm,


homogenized and 30g obtained to make a fire assay
Fire assay is a procedure to melt (~1200 oC) the whole
material with borax, lead oxide and a source of carbon
(e.g. flour). The carbon reduces the PbO and the lead
carries the precious metals to the bottom of the crucible.
The lead button is placed into a cupel, which is a small
dish made from fishbone ash, and placed into a furnace.
Lead volatilizes and soaks into the cupel, leaving a small
"bead" of precious metals.
The bead is leached with aqua regia and analyzed by
atomic absorption spectrometry

Diagnosis Leaching

Diagnosis Leaching

Another subsample of the ground material (200 g) is


leached with cyanide 1 g/L (467 mL) for 24-48 hours
(rolling bottles or agitated beaker) using 30% of solids,
pH 10.5, ambient temperature. During the test, check free
cyanide consumption (titration with AgNO3) and
eventually add more cyanide if needed.

%Au extracted = mg gold in solution (volume was 467mL)

Some people keep the rolling bottles for 72 h, but this


depends on how much coarse gold has the material. You
can pan a bit of the material to check the presence of
coarse (>0,1mm) gold

mg of gold in sample (weight was 200g)


If total gold was not extractedEuse the filtration residue
(now it its dried).
Regrind it, weigh it and leach it again with cyanideEin most
cases this solve the problemEbut the question is how fine
you must grind the material (ore or concentrate)?
It is not suggested to grind too fine since this is a very
expensive operation in a real plant

Filter the solution and send it to be analyzed by atomic


absorption. Wash, dry and keep the residue.

Grind below 200 mesh (0.074mm) and use same leaching


with CN conditions as above

With the result from the atomic absorption you can check
if the total gold was dissolved in cyanide

Filter and send solution to atomic absorption. Wash, dry and


keep the residue.

21

Diagnosis Leaching

Diagnosis Leaching

If the total gold was not extract yet, gold can be occluded
in the sulfide minerals. Weigh the dry residue.

Leach the residue with cyanide using similar conditions


as above. Filter and keep residue.

Fe3+

Oxidize sulfides using 2M HCl and 100 g/L


as FeCl3,
at boiling temp. for 6 to 24 h, L:S=2:1. Use an agitated
beaker.

Send solution to atomic absorption


If the total gold was not extracted yet and the sample has
organic matter (dark color), use the filtration residue from
the previous leaching step

Filter the sample, wash it and keep solution (measure the


volume). If you notice in the wet solids some sulfides, add
on the wet sample nitric acid 1:1 (HNO3 55%: distilled
water) L:S=10:1 (approximately)

Check if gold is adsorbed on organic matter. Extract gold


using 40% v/v acetonitrile in distilled water, 10 g/L
sodium cyanide, and 2 g/L NaOH, 16 hours, L:S =
5:1Efilter, wash and analyze solution. Dry residue.

Filter it, wash it well (measure the volume of solution). All


acid solutions must be analyzed as acid + oxidizing agent
can dissolve some gold (some authors found gold in
solution)

If total gold was not extracted yetEuse filtration residue.


Probably the acetonitrile was not enough to extract all
organic matter

Dry and weigh residue

Diagnosis Leaching
An ultimate test is to burn carbonaceous material off in a
furnace at 700 C for 6 hours and repeat cyanidation.
This can also roast any residual sulfide
Leach silicates with HF and filter. L:S=10:1
Residual gold: leach the residue with aqua regia: 3 HCl +
1 HNO3. L:S=10:1

Environmental Management of
Cyanide

Analyze solutionEnow the total gold was definitely


extracted. Based on the weight of each leaching step
calculate the % gold extracted in each step.
The sequence of leaching can have more steps
depending on the mineralogical phases to be
investigated
Adapted from Lorenzen, L. (1995). Minerals Engineering, v. 8, n. 3, p. 247-256

Use of Cyanide

Use of Cyanide

About 1.4 million tonnes of hydrogen cyanide


(HCN) are produced annually worldwide.
Cyanide price is around US$ 1.1 and 1.3 per
kilogram but now increased to near US$ 3/kg

Gold Mining
13%

Used in
production of
Organic
Chemicals
85%

Other
2%

According to the ICMI International Cyanide


Management Institute, 1.4 million of HCN is
produced annually in the the world. This is
equivalent to 2.5 million tonnes of NaCN.
About 13% is used in the gold mining industry.
This is equivalent to 325,000 tonnes/a of NaCN.

Used for
NaCN
production

ICMI (2010). International Cyanide Management Institute. http://www.cyanidecode.org/cyanide_use.php

22

Gold Uses

Gold Uses

Source: Elma van der Lingen (2005). Golds Other Uses, The LBMA Precious
Metals Conference 2005, Johannesburg, p.75-80

Source: Elma van der Lingen (2005). Golds Other Uses, The LBMA Precious
Metals Conference 2005, Johannesburg, p.75-80

Gold Consumption

Gold Mine Production 2009


(tonnes)
1. China (314)
2. Australia (227)
3. United States (216)
4. South Africa (205)
5. Russia (205)
6. Peru (180)
7. Canada (95)
8. Ghana (90.2)
9. Indonesia (90)
10. Uzbekistan (80)

Total: 2572 tonnes

The total gold produced in


the world: 161,000 tonnes;
enough to fill 2 Olympic
swimming pools
India is the largest gold
consumer. In 2008
consumed 660.2 tonnes Au
In 2008 China consumed
395.6 tonnes of gold

Photo: http://goldprice.org/buyinggold/uploaded_images/indian-gold-742896.jpg

Others (854)

Source: Goldsheet. http://www.goldsheetlinks.com/production.htm

Use of Cyanide
Cyanidation employs diluted sodium or potassium
cyanide solutions containing 50 to 500 mg/L (free
cyanide is typically 50 to 100 mg/L).
Cyanide consumption is typically 300 to 2000 g NaCN
per tonne of ore.
In average 100 tonnes NaCN is used to produce 1 tonne
of gold.
Cyanide concentration in effluents (Canadian gold
industry) range from 0.3 to 30 mg/L (ppm).
Cyanide is also used as a depressant to separate
multiple sulfide ores by flotation (e.g.: depress
chalcopyrite to float galena). Concentration of total
cyanide in flotation effluents is <0.03 mg/L (ppm).

Cyanide Toxicity
Species
Rainbow trout

Yellow perch
Snail

Temperature
(C)
6
10
12
18
15
21
20

96-h LC50 (mg/L)


0.028
0.057
0.042
0.068
0.090
0.102
0.432

Higher temperature, lower toxicity

23

Cyanide Toxicity
Adverse effects on fish swimming and
reproduction usually occur between 0.005 and
0.007 mg of free cyanide/L.
Free cyanide concentrations between 0.05 and 0.2
mg/L are fatal to the more-sensitive species

Cyanide Toxicity
Public perception is that cyanide is very
dangerous...





chemical warfare
judicial executions
mass suicides
the Tylenol affair

A large majority of the public believes that cyanide


is more dangerous than mercury...however cyanide
is not persistent in the environment and Hg is.
Problems:
 spills
 misuse of cyanide by Artisanal Gold Miners

Cyanide Toxicity

Cyanide Toxicity

Jim Jones was the founder


and leader of the Peoples
Temple, in Jonestown,
Guyana
On November 18, 1978,
909 Temple members,
including 276 children,
drunk cyanide with Cool Aid
Source: Infoczarina, 2008

http://www.chicagostagereview.com/wp-content/uploads/2008/09/jonestown1.jpg

Cyanide Spills

Cyanide Spills

Baia Mare, Romania, mine re-opened


in 1999.

1000 tonnes
of fish killed

Intense rain in Jan 2000 = overflow

CN in the
Danudbe

m3

100,000
of tailings with cyanide
released to the river
50 to 100 tonnes of cyanide released

Public
reaction was
horrible

24

Cyanide Spills
1995 Omai Mine in the Esequibo region in Guyana
4 millions m3 of cyanide contaminated tailings entered the
Essequibo River
Until now the use of cyanide in mining is not allowed in
Guyana
The use of Hg has increased

Rudimentary Cyanidation Plant made by


Artisanal Miners in Zimbabwe

Amalgamation
tailings (full of
Hg) are
submitted to
cyanidation

http://www.ec.gc.ca/inre-nwri/default.asp?lang=En&n=0CD66675-1&offset=14&toc=show

Rudimentary Cyanidation Plant made by


Artisanal Miners in Zimbabwe

Misuse of Cyanide
Increasing the use of Hg-amalgamation followed
by cyanidation in Artisanal Mining.
Cyanidation of Hg-rich tailings forms Hg(CN)42which is a very stable and persistent compound.
This can be transformed into highly toxic
compounds, e.g. Methylmercurycyanide

...at least they know that cyanide is dangerous!!!

Artisanal Gold Miners (Sulawesi, Indonesia)

Artisanal Gold Miners (Sulawesi, Indonesia)


Rudimentary tailing pond; often CN-rich
tailings reach the streams

Recovering loaded charcoal (retained in a screen)

Only CN destruction method = NATURAL = sun light


False perception that this destroys all cyanide
complexes

25

Cyanide Toxicity
Free cyanide criteria currently proposed for the
protection of natural resources:
 Free cyanide (CN- or HCN) criteria for the
protection of aquatic life of natural resources:
<0.005 mg/L (Canadian Water Quality
Guidelines, 2001).
 for human protection:
drinking water in USA and Canada: MAC = 0.2 mg/L
in drinking water in Sweden: 0.05 mg/L
WHO Drinking water quality guideline: 0.07 mg/L (12
g/kg body weight)
<50mg/kg in diet
<5mg/m in air

Cyanide Toxicity (humans)

Cyanide Toxicity
The cyanide toxicity depends on the cyanide species. The
predominance of free cyanide (CN- and HCN) depends on
the pH
In solutions with pH
above 10, free cyanide
is as CN- and not as
HCN gas
The gold cyanidation is
usually conducted at
pH 10.5 to 11

Cyanide Toxicity (humans)

In solution, 3 to 5 mg of cyanide/kg body weight is lethal

Cyanide is readily absorbed through inhalation,


ingestion or skin contact.

If a mine uses a CN
solution of 300
mg/L

In respiratory exposure to hydrocyanic acid (HCN


gas), death occurs at 0.1 to 0.3 g/m

A 100-kg person
should drink 1.5 L
to die

Cyanide is a potent asphyxiant. It induces tissue


anoxia through inactivation of cytochrome oxidase
due to the reaction of CN- and Fe3+.
Oxygen cannot be utilized and death results from
the depression of the central nervous system.

You need to drink a lot of Cyanide solution to die

Cyanide Toxicity (humans)


Some plants such as sorghum, cassava, bamboo
and lima beans can contain over 2,000 mg/kg total
cyanide. At this level, ingestion of 170 g of the plant
can be lethal to a 80 kg-human being.

Fishing with Cyanide


Its forbidden to fish with
cyanide and explosives

Congenital hypothyroidism (cretinism) is present in


15% of newborns in certain areas of Zaire where
cassava is a staple food. This incidence is
approximately 500 times that observed in industrial
countries.

Ecuador, 2006

26

Cyanide Toxicity (humans)


Cyanide is detoxified by an enzyme called
rhodanase forming thiocyanate CNS
The major route of cyanide elimination from the
body is via urinary excretion of thiocyanate (CNS).
The toxicity of thiocyanate is significantly less than
that of cyanide, but chronically elevated levels of
thiocyanate in blood can inhibit the uptake of
iodine by the thyroid gland, thereby reducing the
formation of thyroxine.

Cyanide Toxicity (humans)


Organs affected by Chronic intoxication with cyanide
(oral exposure):

Central nervous system: neuropathies and


amblyopia (partial or complete loss of vision in one
eye caused by conditions that affect the normal
development of vision)
Thyroid: increase thyroid weights and depress
thyroid function
Reproduction and Development: congenital
hypothyroidism was reported in human newborns

Cyanide Toxicity (humans)


Cyanide does not accumulate in the blood and
tissues following oral exposure to inorganic
cyanide and no cumulative effect on the
organism during repeated exposure has
been demonstrated.
There is a cumulative effect of exposure to
thiocyanate resulting in thyroid toxicity,
including goitre and cretinism.

Cyanide Toxicity (humans)


Organs affected by Chronic intoxication with cyanide
(inhalation):

Central nervous system: vertigo, equilibrium


disturbances, nystagmus, nervousness, headache,
weakness, loss of appetite, changes in smell and
taste
Cardiovascular and/or respiratory system:
breathing difficulties
Gastrointestinal tract: nausea, and gastritis
Thyroid: Enlarged thyroids
Reproduction and Development: risk of giving birth
to low body weight infants and of perinatal death.

Kidneys

Cyanide Toxicity (hypothyroidism)


The main purpose of thyroid hormone is to "run the body's
metabolism. It takes iodine, found in many foods, and
convert it into thyroid hormones.
Hypothyroidism results in inflammation of the thyroid gland
and reduction of hormone production.

Cyanide Toxicity
(congenital hypothyroidism)
Cretinism:
Poor length growth
Adult stature without
treatment ranges
from 1 to 1.6 m
Neurological
impairment
Thickened skin

goitre
Sources: http://www.endocrineweb.com/thyfunction.html
http://en.wikipedia.org/wiki/Goitre

thyroid gland
normally weighs
<30g

Enlarged tongue
Protruding abdomen

Sources:
http://www.gidabilimi.com/images/kretenizm1.png
Wikipedia

27

Important Toxicological Facts


The greatest source of cyanide exposure to
humans and some animals is cyanogenic food
plants and forage crops, not mining operations.
Free cyanide is the primary toxic agent
Cyanides are not mutagenic or carcinogenic.
There is no indication that cyanide is
biomagnified in food web.
Cyanide has low persistence in the environment
In general, the toxicity of free cyanide is
reduced when a complex is formed.

Free Cyanide
Determined by tritation with AgNO3
Silver will complex with free CN and excess of Ag+ is
detected by p-dimethylaminobenzalrhodanine or by
potassium iodide (KI) whihc are indicators
AgNO3 + 2NaCN = NaAg(CN)2 + NaNO3
Color will change from yellow to blue (dimetyl) or a white
bluish color in the case of KI
Free cyanide is determined based on the volume of
silver nitrate used in the titration
Total CN is determined by another method... distillation

Fate of Free Cyanide


Free cyanide seldom remains biologically available in
soils and sediments because it is either complexed by
trace metals, metabolized by various microorganisms,
or lost through volatilization.
Under aerobic conditions, cyanide salts in the soil are
microbiologically degraded to nitrites or form complexes
with metals.

Types of Cyanide
1. Free cyanide (HCN/CN-) and simple cyanide salts
(NaCN, KCN) which dissolve in water to form free
cyanide. Free cyanide is the active form to leach gold
2. Weak and moderately strong cyanide complexes such
as cyanides of Zn(CN)42-, Cd(CN)3-, Cd(CN)42-, Cu(CN)2-,
Cu(CN)32-, Ni(CN)42-, Ag(CN)2- These cyanides are known
as Weak Acid Dissociable Cyanides (WAD) as they can
be decomposed in weak acid (pH 3 to 6).
3. Strongly bound cyanide complexes such as Co(CN)64-,
Au(CN)2-, Fe(CN)64-. These are stable under ambient
conditions of pH and temperature

Complexes with Heavy Metal


In the leaching of gold, many other metals can be
dissolved in cyanide forming complexes.
Example of minerals soluble in cyanide:

Pyrrhotite - FeS
Argentite - AgS
Malachite - CuCO3.Cu(OH)2
Chalcocite - Cu2S
Bornite - Cu5FeS4
Orpigment - As2S3
Galena - PbS, partially soluble
Sphalerite - ZnS, partially soluble
Pyrite - FeS2, sparingly soluble

Main Cyanide Reactions


Hydrolysis
Oxidation of HCN/CN-

CN- + H2O = HCN + OH2HCN + O2 = 2HCNO


2CN- + O2 + catalyst = 2CNO-

Hydrolysis of CNO
HCNO + H2O = NH3 + CO2
Hydrolysis/saponification of HCN + 2H2O = NH4COOH or
HCN + 2H2O = NH3 + HCOOH
HCN
Aerobic biodegradation

2HCN + O2 + enzyme = 2HCNO


S 2x + CN- = S 2x 1 + CNS

Under anaerobic conditions, cyanides denitrify to


gaseous nitrogen compounds and enter the
atmosphere.

Thiocyanate formation

All cyanide complexes are subjected to (biotic and


abiotic) oxidation.

Metal-cyanide complexation

Zn2+ + 4CN- = Zn (CN ) 24

Anaerobic biodegradation

CN- + H2S = HCNS + H+


HCN + HS- = HCNS + H+

Cyanide compound
dissociation

S 2 O 32 + CN- = SO 32 + CNSNaCN = Na+ + CN-

28

Cyanide Treatment Processes

Cyanide Cycle

Natural Degradation (Lagooning)

NH3 + CO2
HCN/CNcyanidation
tank

Oxidation Processes

evaporation and
decomposition

Alkaline Chlorination

spill
tailing pond

River
NH3 + HCO3or

tailing with cyanide


HCN/CN-

Fe(CN)63Fe(CN)64-

NO3-

Electrochemical Processes
Ozonation
Hydrogen Peroxide

CO32-

INCOs SO2/Air Process


CH4 + CO2

Precipitation (Cuprous Process)

Natural Degradation

Cyanide Treatment Processes (cont.)


Conversion to Less Toxic Forms
Biological Treatment
Cyanide Recovery Processes

It is the oldest treatment method used by Canadian


gold mines to remove cyanide from effluents.
Volatilization is the main mechanism. The most
important variables are:

Acidification/Volatilization/Reneutralization AVR

pH
temperature

Ion Exchange

UV light
aeration

Activated Charcoal

Other variables:

Electrolytic Processes

Natural Degradation
The equilibrium between free cyanide species (CNand HCN) is pH dependent: HCN = H+ + CNDissociation
constant

[ H ].[ CN ]
= 4 .93 x10 10
[ HCN ]
Molecular HCN has high vapor pressure and
therefore can readily be volatilized to the
atmosphere. At pH 7, 99.5% of free cyanide exists
as molecular HCN.
Kd =

(CN-/HCN)

Free cyanide
is rare in mining tailings
because of the high reactivity of the CN- molecule
with metal ions.

biodegradation
precipitation
conversion to thiocyanate

Stability of Cyanide Complexes


Cyanide Complex
Co(CN) 4
6

Dissociation Constant
10-50

Fe(CN ) 4
6

10-47

Hg( CN ) 2
4

10-39

Au( CN ) 2

10-37

Cr ( CN ) 3
6

10-33

Cu( CN ) 24

10-30.7

Ni( CN ) 2
4

10-30

Cu( CN ) 23

10-29.2

Cr ( CN ) 4
6

10-21

Zn( CN ) 2
4

10-21

Ag( CN ) 2

10-20.4

Cd ( CN ) 2
4

10-19

29

Natural Degradation

3
4
Ferrocyanides ( Fe( CN ) 6 ) and Ferricyanides ( Fe (CN ) 6 )
are very stable compounds. They can form complexes with
trace metals. Most complexes are insoluble, e.g.:
SnFe (CN ) 6 = tin(IV) ferrocyanide

Cyanide Guidelines (Canadian Legislation)

Water Use

Strong-acid
dissociable
cyanide plus
thiocyanate
g/L (as CN)

Strong-acid
dissociable
cyanide
g/L (as CN)

Weak-acid
dissociable
cyanide
g/L (as CN)

Raw Drinking Water


(maximum)

200 g/L

Not applicable

Not applicable

Fe 4 [ Fe( CN ) 6 ]3 = ferric ferrocyanide


Co 3[ Fe( CN ) 6 ]2 = cobalt ferricyanide

Sn 3 [Fe(CN ) 6 ]2 = tin(II) ferricyanide

Major environmental concern:

ferrocyanides and ferricyanides (usually


in the sediments) can form free cyanide by
influence of ultraviolet light
This reaction can take hundreds of years

Freshwater Aquatic Life


(30-day average)

Not applicable None proposed

< or =
5 g/L

Freshwater Aquatic Life


(maximum)

Not applicable None proposed

10 g/L

Marine and Estuarine


Aquatic Life
(maximum at any time)

Not applicable None proposed

1g/L

British Columbia Approved Water Quality Guidelines


(Criteria) 1998 Edition

Cyanide Guidelines
The Canadian MMER (Metal Mining Effluent Regulation,
2002): maximum level of total cyanide to be released in a
mining effluent is 1.0 mg/L (ppm) as a monthly average
concentration, 1.5 mg/L in a composite sample and 2 mg/L
in a grab sample.
In Yukon Territory, the discharge limits are 0.5 mg/L of total
cyanide and 0.2 mg/L of WAD (weakly acid dissociable)
The World Bank guidelines (1995) for discharge into the
environment are:

Free Cyanide: 0.1 mg/L

Weak Acid Dissociable: 0.5 mg/L

Total Cyanide: 1.0 mg/L.

In no case should the concentration in the receiving water


outside of a designated mixing zone exceed 0.022 mg/L.

Natural Degradation
Natural degradation is:
 suitable for removal of free cyanide,
 removes partially Zn and Cd cyanide
complexes and thiocyanate (CNS)
 does not remove Cu and Ni complexes and
Iron-cyanides.
Natural degradation is more effective when barren
solutions (barren bleed ponds) are stored
separately from solid tailings in shallow ponds.

Natural Degradation
Before the mid 1970s, natural degradation was the
only treatment method used by the Canadian
mining industry
Photodegradation is affected by turbidity, color and
depth, intensity and wavelength of light, angle of
light incidence and cloud cover.
Degradation: free cyanide in the concentration
range of 0.1 to 0.5 mg/L is volatilized at a rate of
0.021 mg CN/ft2.hr in still waters.
Rates in agitated water are up to 3 times as great.
A temperature increase of 10C causes the free
cyanide removal rate to increase by more than 40%

Oxidation by Chlorine
Alkaline chlorination is the oxidation of cyanide in an
alkaline solution by chlorine or hypochorite.
The complete oxidation of cyanide proceeds in two
stages at different pHs:
In the first stage, cyanide is transformed to cyanate
(CNO) (which is considered approximately onethousandth as toxic as hydrogen cyanide). The
oxidation of cyanide is represented by the equations:
Any pH:
High pH:

CN- + Cl2 = CNCl + Cl-

CNCl + 2OH- = CNO- + Cl- + H2O

With hypochlorite: CN- + OCl- = CNO- + Cl-

30

Oxidation by Chlorine

Oxidation by Chlorine

Advantages of the process:


 Easy to operate
 Reactions reasonably rapid
 Free and WAD cyanides as well as
thiocyanates are destroyed
 Chlorine or hypochlorite readily available in
several forms
 Capital outlay relatively low

The second stage consists of cyanate being


converted to bicarbonate and nitrogen:
2CNO- + 3Cl2 + 4H2O = (NH4)2CO3 + 3Cl2 + CO32(NH4)2CO3 + 3Cl2 + 6OH- + CO32- = 2HCO3- + N2 + 6Cl- + 6H2O

Oxidation by Chlorine
Disadvantages:
 High operating cost (reagents are costly)
 Requires pH control to prevent cyanogen
chloride which is highly toxic
 Ferro and Ferricyanides are not destroyed
 High content of chloride and chlorine in
effluents
 Some chlorination products (e.g. Nahypochlorite, chloro-lime, etc.) are degradable:
storage problems in remote regions.

Electrochemical Processes
Electroreduction: Complex metal cyanide ions reduce at the cathode to deposit or
precipitate the metal, regenerating free cyanide:
Me( CN ) 2n n + 2 e = n CN + Me
( Me = divalent metal)
Electrochlorination :
Anode reaction:

Cl = Cl + e
2Cl = Cl 2 (g)

Cathode reaction:

H 2 O + e = H + OH
2 H = H 2 (g )

Introducing NaCl into the solution, chlorine is produced by


electrolysis. Hypochlorite and chlorate can also be formed. Free
cyanide, WAD cyanides and thiocyanates are destroyed. Ironcyanides are not destroyed

Cyanide can be regenerated

Oxidation with Hydrogen Peroxide

Oxidation with Hydrogen Peroxide

Cyanide oxidation with H2O2 is a fast, one-step


reaction, forming non-toxic intermediates.

Cu and Ni cyanides are partially destroyed and


Iron-cyanides are partially precipitated.

H2O2 oxidizes free and Zn & Cd cyanides to


cyanate which is further hydrolyzed yielding
biodegradable ammonia and carbonate.

Since copper and other metal ions are already in


many mining effluents, additional metallic catalyst
may not be required to enhance the reaction rate.

CN- + H2O2 = CNO- + H2O


(Cu2+

is a catalyst)

CNO- + 2H2O = NH4+ + CO32-

Degussa process uses borate compounds as


catalysts resulting in a substantial saving of
hydrogen peroxide consumption (up to 60%).

(pH just < 7)

31

Oxidation with Hydrogen Peroxide

Oxidation with Hydrogen Peroxide


(Example)

There are a variety of processes combining hydrogen


peroxide with other compounds, such as glycolonitrile
(Kastone process), H2SO4 (Caros acid), SO2, etc.

Species

Formation of thiocyanate by H2O2 is slow (in contrast to


chlorination).

As
Cu
total CN
Fe
Se
Ag
Zn

H2O2 consumption is estimated to be around 3 kg/kg


CN-. Theoretical dosage: 1.5 kg H2O2/kg CN The process is not very suitable for slurries.
High operating cost.
First used at Ok Tedi in 1984 and in Canada at Teck
Corona in 1985. Many plants in Canada use peroxide.

Invented by INCO in 1984 as a result of a research to destroy cyanide


used to depress pyrrhotite during flotation of pentandite (NiFe9S8) and
Chalcopyrite (CuFeS2).

A mixture of sulphur dioxide and air rapidly oxidizes free cyanide and
WAD metal cyanide complexes in the presence of Cu2+ as catalyst.
-

INCO SO2/Air Process

Copper should be present in minimum concentration of 50 mg/L and


can be added as copper sulphate. Cu2+ additions depend on the iron
content of the effluent and are in the range 0 to 0.5 g/g total CN.

Free cyanide, Zn, Cd, Cu, Ni cyanides are destroyed. Iron-cyanides


are partially precipitated. Thiocyanide is partially (10 to 20%)
destroyed.

The process is usually performed in one or two stages, bubbling


SO2-air or adding sodium metabisulphite. Air flowrate is around 1
L/min per liter of solution. In practice 3-4 kg SO2 (or 5-8 kg of sodium
metabisulphite) is required per kg of cyanide. Stoichiometrically the
reactions require 2.46 kg SO2 per kg of WAD cyanides.

Retention time ranges from 20 min to 2 hours.

CN + SO2 + O2 + H2O = CNO + H2SO4


(Cu2+ is a catalyst)

Me(CN) 24 + 4 SO 2 + 2 O 2 + 4H 2 O = 4 CNO + 4 H 2SO 4 + Me 2+


Me2+ = Zn2+, Cu2+, Ni2+, Cd2+, etc.
(neutralization): H2SO4 + Ca(OH)2 = CaSO4.2H2O
(pH>8)
(precipitation): Me2+ + Ca(OH)2 = Me(OH)2 + Ca2+
2 Me 2 + + Fe(CN ) 64 = Me 2 Fe(CN ) 6

INCO SO2/Air Process


The process has been licensed at over 100 project
sites worldwide.
The process has been used to treat effluents
containing > 200 mg/L total cyanide and routinely
reduces this to <1 mg/L
Capital cost for an installation to destroy 3,000
tonnes of slurry/d is Cn$ 1.2 million (installed)
Typical operating cost to treat tailings from a plant
using CIP is Cn$0.8/tonne
Patent expired in 2004

EPA dws
(mg/L)
0.05
9.0
0.05
0.3
0.01
0.05
5

Note: H2O2 dosage = 2.5 mL/L


dws = drinking water standard

INCO SO2/Air Process

Effluent (mg/L)
Before
After
0.2
<0.05
4.5
<1
280
3
16
<0.015
5
4
3.2
1
157
<1

INCO SO2/Air Process


Species
Total cyanide
WAD
cyanides
Cyanate
Thiocyanate
Cu
Fe
Ni

Liquid Effluent (mg/L)


Before
After
365.8
0.69
225
0.15
44.6
100.7
35.45
45.82
4.13

324.2
82.5
1.21
0.26
0.25

Final Tailing
(mg/L)
29.4
12.2
52.9
18.9
7.7
5.35
0.51

32

Combinox Process
Developed in Germany by CyPlus, this is a variation of
the INCO Process, when the patent expired (May
2008)
This process is a combination of SO2/Air and Peroxide
(Degussa Process)
Thiocyanate (CNS) is destroyed
It destroys free and Zn, Ag, Cd, Cu, Ni cyanides
Fe cyanides are precipitated in presence of copper:
Fe(CN)64- + 2Cu2+ Cu2Fe(CN)6 (solid)
Final product: CO2 + NH4+
It is considered one of the most effective cyanide
destruction processes

Combinox Process

Applied in Las Crucitas Project, in Costa Rica


7500 tonnes/day of saprolite
In the future 5000 tonnes/d hard rock (1.5-2 g/t)
All material is leached with 150-200 mg/L CN: CIP
Compound (mg/L)

First applied in 1984 at Homestake Lead Mine, South


Dakota to treat 800 t/h of mixed mine water and
tailings.
Sensitive to temperature (optimum: 30 C, pH 7 8.5).
Process requires gradual acclimatization of mutant
strains of bacteria (Pseudomonas) to the high
concentration of cyanides and thiocyanate.
Oxidation rate of cyanide to cyanate is increased by the
bacteria.

0.58

0.03

Free CN

<2

<0.02

0.31

<0.01

WAD CN (moderately
complexed)

Cyanide Recovery
Acidification - Volatilization - Reneutralization AVR
Processes was used successfully at Flin Flon (Canada)
from 1930 to 1975 and in several other commercial
operations.
The process consists of acidification of the alkaline
cyanide leach solution producing hydrogen cyanide
(HCN) which is removed by volatilization in a stream of
air to be reabsorbed into an alkaline solution.

The Cyanisorb is an AVR process that uses high


efficiency packed towers, low pressures and moderate
pH levels. It recovers about 90% of the cyanide from
tailings: Gold mine in Waihi (New Zealand), AngloGold
in Argentina, DeLamar (U.S.), Marlin Mine (Guatemala)
are using Cyanisorb method

CN- + H+ = HCN

Acidification:

Absorption: 2HCN + NaOH = NaCN + 2H2O

Cyanide Recovery
Golconda (Australia) has reduced the total cyanide
concentration in effluents from >200 mg/L to < 5 mg/L.
Reagent consumption is 0.6 kg H2SO4/t solution and
0.45 kg NaOH/t. Cyanide recovery 50 to 85%.

Solution after 10
days

Total CN

Biological Treatment
Cyanide is degraded by aerobic and anaerobic
microbes

Solution after
Combinox

Cyanisorb Process
Barren solution

300 ppm HCN

HCN ladden air

H2SO4

bleed air

10%

air

pH 5 - 7.5
Ca(OH)2

AVR technology has been developed to allow


treatment of slurry streams directly without the need for
solid-liquid separation.

stripped slurry
NaCN (recovered)
solution

Pulp to tailing pond

Metals precipitation

33

Cyanide Recovery: Ion Exchange


Developed in the mid-1950s for the recovery of cyanide
from electroplating solutions.
Resin impregnated with copper (to tie up all free cyanide as
complex) precipitates cuprous cyanide in the resin matrix.
Strong-base anion exchange resins remove cyanide
complexes of iron, zinc, copper, nickel, cobalt, gold and
silver can be removed effectively followed by elution of the
resin.
Practical problems:
 Efficient elution of all species that load onto the resin is
hard to achieve
 Resin must be regenerated or new resin must be used to
maintain process efficiency
 High costs involved

You and me, we used to mine together


Cyanide together, always
I really felt, a bitter almond smell
When the pH fell, and I ran
You dont know, where the pH goes
10.5 is good to leach the gold
Don't leach if you dont have control
pH cannot be low
Be careful cause it hurts
Don't leach if you forgot the lime
the smell can be sublime, but
Be careful cause it hurts

Cyanide Recovery: Activated Charcoal


Activated Charcoal has been used for
recovery of metals from cyanide solutions.
Activated charcoal is capable of adsorbing
up to 5 mg CN-/g from aerated alkaline
cyanide solutions. This can reach 25 mg CN/g in the presence of a catalyst such as
copper.
Cyanide can be recovered (elution) from the
AC into low ionic strength solution at
elevated temperature.

In long term, the cyanide effect,


A lump in your neck, you will cry
Thyroidism, this can appear
And them it will be to late youre gonna die
Don't leach gold or even silver,
Dumping cyanide in rivers
Be careful cause it hurts
Don't leach if you think the fish wont feel
Cyanide in their gills, Be careful cause it hurts
You dont agree, but with 5 ppb, fish can die

You told me, youve never had destroyed


The cyanide you have employed, you fool
Youve just trust, what the sun can do
Youve just left the tailings in a pool
Don't leach what youre doing is quite insane
Cyanide still remains
Be careful cause it hurts
Don't leach I dont need your reasons
Telling this is sunny season
Be careful cause it hurts
THE END

34

You might also like