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Studying Gold Ores: Mineralogy, Cyanidation, Toxicity and Environmental Issues
Studying Gold Ores: Mineralogy, Cyanidation, Toxicity and Environmental Issues
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
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
%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
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
GANGUE
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
Scrubbing
Free gold
Cyanide
Leach
Comminution
Gold
Comminution
Gravity
Sep
Free gold
Flotation
Oxidation
Cyanide
Leach
Free gold
Cyanide
Leach
Gold
Brazil, 2006
Mining coluvial gold ore
in the Amazon
25 m
Gold
25 m
Ga
Chalcopyrite
CuFeS2
Au
Si
Reflected light
Reflected Light
gold
gold
chalcopyrite
gold
increasing liberation.
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
- 20 min.
- 30 min.
Batch
Flotation
28
20
Grinding
(various time)
- no grinding
- 5 min.
- 10 min.
28
#
grinding time
20
#
Composite
Sample
3
2.5
48
#
Example
35
#
48
35
Mesh
Gold distribution in screened fractions
100
100
90
%Gold
recovery
80
by
concentration 70
80
grinding time
60
40
1 min
5 min
10 min
20
20 min
0
16
60
20
28
35
48
65
100
150
200
270
400
-400
Tyler Mesh
50
0
10
20
30
+
wire
Battery
12 V
Graphite rod
Mercury
Brazil, 2006
Zimbabwe, 2006
Amalgamation Barrel
Ecuador, 2004
Indonesia, 2006
ATTENTION:
Results:
Screening
light fractions
Heavy Liquid
Separation
heavy fractions
amalgams
Amalgamation
residue
Cyanidation
(*)
(*)
(10g/L NaCN,
NaCN, pH=10, 40%sol, 24 h)
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
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
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#
sub-sample
Crushing
DAu (%)
100
25
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
Cyanidation
Fusion:
Cyanidation:
Amalgamation:
11.4 %
64.0 %
24.6 %
residues
Fire Assay
= splitting
= optional
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
Name
Discovery
6th
Century
Jabir
Hayyan
1704
Gold Cyanidation
1774
C.W.
Schule
1852
K.F.
Plattner
Early
1700s
P.J.
Discovered potassium ferrocyanide
Macquer (K4[Fe(CN)6]) by combining Prussian Blue with
Alkali (KOH)
1782
C.W.
Schule
Date
Name
1811
J.L. GayLussac
1834
1840
Elkington
1846
L. Elsner
1887
Discovery
Determined Blue Acid was HCN
J.S.
MacArthur,
R.W.
Forrest,
W. Forrest
Cyanide Stability
pH of Gold Cyanidation
bitter
almond
smell
Au Dissolution Rate
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.
10
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.
11
Preg-Robbing Ore
Preg-Robbing Ore
Preg-Robbing Ore
Preg-Robbing
Ore
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
Columns with AC
Au rich solution
AC
Electrolysis
Electrolysis
Elution
Gold
Gold
Electrolysis
Au rich solution
Gold
AC = activated chacoal
12
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
13
CIP
Cyanide Destruction
solution
AC
Tailings Pond
Elution
Electrolysis
Gold
solution
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)
Re-cycle to Process
Comminution
Cyanide Leach
pulp
pulp
S/L Separation
Settling Tank
pulp
solution
solution
pulp
Precipitation w/ Zn
Cyanide Destruction
Tailings Pond
pulp
Precipitate w/Al
Gold
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
Static leaching
Gekko
Acacia
Mill-leaching (cyanidation in a small ball-mill)
Ecuador, 2009
Ecuador, 2009
15
Ecuador, 2007
Cyanidation in Vats
Ecuador, 2007
Cyanidation in Vats
Vat-leaching
tank
Pool with CN
solution
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
Intensive Cyanidation
Intensive Cyanidation
17
Intensive Cyanidation
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
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
Intensive Cyanidation
Intensive Cyanidation
Acacia System:
Knelson Centrifuge
provide concentrates
for the reactor
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
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
-2mm
Icon centrifuge
tailing
Icon centrifuge
tailing
flotation
co
nc
.
conc.
.
nc
co
Intensive
Cyanidation
activated
charcoal
elution
final
tailing
electrolisis
meting
gold
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
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.
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
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
Ecuador, 2007
20
Diagnosis Leaching
This is a procedure to assess why the gold is not being
extracted by classical cyanidation (low CN concentration
and no peroxide)
Diagnosis Leaching
Diagnosis Leaching
With the result from the atomic absorption you can check
if the total gold was dissolved in cyanide
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.
Fe3+
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
Use of Cyanide
Use of Cyanide
Gold Mining
13%
Used in
production of
Organic
Chemicals
85%
Other
2%
Used for
NaCN
production
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
Photo: http://goldprice.org/buyinggold/uploaded_images/indian-gold-742896.jpg
Others (854)
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
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
Cyanide Toxicity
Cyanide Toxicity
http://www.chicagostagereview.com/wp-content/uploads/2008/09/jonestown1.jpg
Cyanide Spills
Cyanide Spills
1000 tonnes
of fish killed
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
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
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
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
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
If a mine uses a CN
solution of 300
mg/L
A 100-kg person
should drink 1.5 L
to die
Ecuador, 2006
26
Kidneys
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
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
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
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
Hydrolysis of CNO
HCNO + H2O = NH3 + CO2
Hydrolysis/saponification of HCN + 2H2O = NH4COOH or
HCN + 2H2O = NH3 + HCOOH
HCN
Aerobic biodegradation
Thiocyanate formation
Metal-cyanide complexation
Anaerobic biodegradation
Cyanide compound
dissociation
28
Cyanide Cycle
NH3 + CO2
HCN/CNcyanidation
tank
Oxidation Processes
evaporation and
decomposition
Alkaline Chlorination
spill
tailing pond
River
NH3 + HCO3or
Fe(CN)63Fe(CN)64-
NO3-
Electrochemical Processes
Ozonation
Hydrogen Peroxide
CO32-
Natural Degradation
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
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
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)
200 g/L
Not applicable
Not applicable
< or =
5 g/L
10 g/L
1g/L
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:
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:
30
Oxidation by Chlorine
Oxidation by Chlorine
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 )
is a catalyst)
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Species
As
Cu
total CN
Fe
Se
Ag
Zn
A mixture of sulphur dioxide and air rapidly oxidizes free cyanide and
WAD metal cyanide complexes in the presence of Cu2+ as catalyst.
-
EPA dws
(mg/L)
0.05
9.0
0.05
0.3
0.01
0.05
5
Effluent (mg/L)
Before
After
0.2
<0.05
4.5
<1
280
3
16
<0.015
5
4
3.2
1
157
<1
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
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.
CN- + H+ = HCN
Acidification:
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
H2SO4
bleed air
10%
air
pH 5 - 7.5
Ca(OH)2
stripped slurry
NaCN (recovered)
solution
Metals precipitation
33
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