Hydrometallurgy

5 Leaching Processes
Fathi Habashi
Department of Mining, Metallurgical, and Materials Engineering

Laval University, Quebec City,,Canada

Fathi.Habashi@arul.ulaval.ca

Leaching Processes

Leaching of Metals

Gold & Silver

CYANIDATION 1
The dissolution of gold and silver in
cyanide solutions was one of the puzzles
that faced metallurgists for many years for
two reasons:

Gold, the most noble metal that dissolved only

in aqua regia, dissolved readily in a very dilute
solution of sodium cyanide.
Although gold did not tarnish in air, air was
essential for its dissolution.

Cyanidation 1
Cyanide is derived from Greek
meaning blue, because hydrocyanic acid
(blue acid) was derived for the first time
from Prussian blue pigment when heated
with sulfuric acid.

Cyanidation 2
3.5
Gold

Rate (mg sq in1 hr1 )

3.0
2.5
2.0

Silver

1.5
1.0
0.5
0
0

0.1

0.2

0.3

0.4

0.5%

NaCN concentration

Cyanidation 5
According to this stoichiometry,
stoichiometry, 1 gram mole of oxygen
and 4 gram moles of NaCN should be present in
solution. At room temperature and at atmospheric
pressure, 8.2 mg O2 are dissolved in 1 liter of water. This
corresponds to 0.27 x 103 mol/L. Accordingly, gold
dissolution should occur at a concentration of NaCN
equal to 4 0.27 x 103 49 = 0.05 g/L or 0.005%. Thus
a very dilute sodium cyanide solution would be enough
for dissolving gold.
The fact that oxygen was necessary for dissolution was
not readily recognized because as seen from the above
calculations, oxygen in solution as a result of air
solubility is enough to bring about the reaction.

Cyanidation 6

Cyanidation 7
30
Rate (mg cm in2 hr1 )

7.48 ATM
20

3.40 ATM
10

0
0

0.02

0.04

0.06

NaCN concentration

Rate =

2 A D CN- D O 2 [CN-] [O2]

{D CN - [CN-] + 4 D O 2 [O2]}

Cyanidation 8
It is essential that the cyanide solution be kept alkaline during leaching
to prevent the formation of HCN

Concentration, %

100
80
HCN

CN

60
40
20
0

8
pH

10

12

14

Cyanidation 9
It is essential that the cyanide solution be
kept alkaline during leaching to prevent
the formation of HCN which is extremely
poisonous gas.
Hydrogen cyanide may form as a result of
absorption of atmospheric CO2:
CO2 + H2O H2CO3
H2CO3 + CN HCN + HCO3

Cyanidation 10
25 103

Rate of dissolution
g mol cm2sec1

Gold
20
15
10
Silver
5
0
103

102
[KOH]

101
g mol/L

1.0

20

3
NaOH
2
Ca(OH)2
1
Gold
10

11

12

pH

13

Rate (mg cm2hr1)

Rate (mg cm2hr1)

Cyanidation 11

14

KOH
10
Ca(OH)2
Silver
0
10.8

11.8

pH

12.8

150
140
130
120
110
100
90

20

40
60
Temperature, C

80

100

Cyanidation 13
Leaching
agent

Recycle

Weight of gold dissolved/unit time

Cyanidation 12

Bleed

Ore

Leaching

Filtration

Residue

Recovery

Metal

Recovery of Cyanide
Acidification and recovery of HCN
When SO2 is bubbled in bleed solutions, HCN
is formed: It can be collected and absorbed in a
solution of NaOH to form NaCN for recycle:

CN + H+ HCN

Recovery of HCN

10

Destruction of Cyanide
While the cyanide ion is highly poisonous, its
oxidation product, the cyanate ion, is not.
Chlorine is usually used as oxidizing agent for
this purpose:

Cyanidation
Recent Advances

Heap leaching
Treatment of refractory ores
Cyanidation under pressure

11

Refractory Gold Ores 1

Gold locked up in pyrite or arsenopyrite
crystals, unresponsive to cyanidation
Roasting followed by leaching
Hydrometallurgical approach
Bacterial leaching
Aqueous oxidation in autoclaves

12

Refractory Gold Ores 3

Barrick Gold, Elko, Nevada

Refining of Gold
Hydrometallurgy
Pyrometallurgy
Electrometallurgy

13

Refining
Separation of gold from silver and other
impurities (Cu, Pt metals, etc.) is usually carried
out by electrolysis or by chlorination. However,
on a small scale, e.g., in mints, refining is done
by selective leaching.
The method used depends on the gold content
as well as on the type of impurities present.
While silver is soluble in both nitric and sulfuric
acids, and gold is insoluble, yet these acids
cannot be used to dissolve silver away from an
alloy containing more than 25% Au.

For high-gold alloys

Aqua regia is therefore used. In such alloys, gold is
leached, while silver forms an insoluble residue.
Gold is soluble in aqua regia, but a goldsilver
alloy containing more than 8% Ag cannot be
attacked due to the formation of an insoluble layer
of AgCl.
Therefore, the aqua regia leaching process is used
only for refining high-grade bullions, where the
silver does not amount to more than 8%, or to
cases where the bullion contains enough copper to
open it up to attack in spite of the silver present.

14

Alloy
composition [%]

Low-gold
bullion

High-gold
bullion

Attack by
Remarks

Ag

Au

HNO3 or
H2SO41

Aqua
regia2

100
75

0
25

Bullion treated by
HNO3 or H2SO4.

70
50
25
10

30
50
75
90

Bullion must be alloyed

with Ag before
treatment with HNO3
or H2SO4.

8
0

92
100

Bullion treated by aqua

regia.

Ag is soluble but Au is insoluble.

Au is soluble but Ag is insoluble due to the formation of AgCl.

In both cases, the bullion is first melted

and poured in water to obtain granules
suitable for leaching.

15

Platinum Metals 1
Native platinum ores
Gold ores: Platinum metals enriched in the anodic
slimes

Copper and nickel sulfide ores: Platinum

metals concentrated in the following fractions:

In the magnetic fraction separated from the

sulfide matte
In anodic slimes of copper or nickel
electrolytic refining

Platinum Metals 2
Aqua regia, also known as royal water or eau rgale
because it can solubilize gold the most noble metal
A mixture of one part concentrated nitric acid and
three parts concentrated hydrochloric acid
The dissolving action is due to the formation of
chlorine and nitrosyl chloride:
2Cl Cl2 + 2e
4H+ + NO3 + 2e NO+ + 2H2O
Overall reaction:
HNO3 + 3HCl Cl2 + NOCl + 2H2O

16

Platinum Metals 3

Platinum Metals 4

17

Platinum Metals 5

Platinum Metals
Aqua
regia

Platinum
metals
concentrate

Leaching
FeSO4
solution

Filtration

Ru, Rh, Ir and Os concentrate

Residue

Au precipitation
Filtration
NH4Cl

Gold sand (washing, melting, anode

casting and electrolysis)

Residue

(NH4)2[PtCl6]
precipitation
Filtration

Calcination

Formation of
[Pd(NH3)4]Cl2

Crude
Pt sponge

Aqua regia

NH4Cl

Leaching

Precipitation

NH4OH

Calcination

Pure
Pt sponge

HCl
Precipitation of
[Pd(NH3)2]Cl2

HCl

Fe

Filtration

Leaching

Cementation

Cementation

Recovered traces
of Pt and Pd
from solution

Residue

Zn

Pd
concentrate

To waste

18

Copper, Nickel, and Cobalt

Selective dissolution from low-grade ores by
aqueous ammonia in presence of air (or
oxygen) to form the ammine complexes
[M(NH3)n]2+
Ammonium hydroxide is selected in
preference to H2SO4, which is less expensive
for two reasons:
Presence of excessive acid-consuming gangue such as limestone
or dolomite in the ore
Presence of an iron oxide matrix which partially dissolves in acid
and makes the separation of the metal values difficult

Ammonia Leaching
The dissociation of ammonium hydroxide is small:
NH3 + H2O ' NH4+ + OH
NH3 can be considered as the active complexing agent.

M M2+ + 2e
Complex formation: M2+ + nNH3 [M(NH3)n]2+
Oxidation:

Overall reaction:

M + nNH3 + 1/2O2 + H2O [M(NH3)n]2+ + 2OH

19

Recovery from Leach Solution 1

Solution is boiled to distill off excess
ammonia and to decompose the ammine
complex to precipitate a hydroxide or a
basic carbonate:
[M(NH3)n]2+ + 2OH M(OH)2 + nNH3
2[M(NH3)n]2+ + 2OH + CO32
M(OH)2MCO3 +
2nNH3

Recovery from Leach Solution 2

The precipitate is filtered, washed, and

calcined to yield a high-grade oxide
containing 7578% metal
The gases evolved are absorbed in water
and recycled.
Ammonia retained in the gangue residue is
recovered by steam stripping
Instead of calcination, the precipitated basic
carbonate is sometimes dissolved in
ammonium sulfate solution and the pure
metal is precipitated by hydrogen under
pressure

20

Nickel & Cobalt 1

Laterite nickel ores at Nicaro in Cuba, at
Marinduque in the Philippines, and at Greenvale
in Australia containing much acid-soluble
gangue are first reduced then leached with
ammonia.
Manganese nodules found on ocean floor
containing about 1% Cu and 1% Ni. It was
suggested to recover copper and nickel from this
source by reducing the nodules then leaching
selectively by ammonia.

Nickel & Cobalt 2

Oxidation of iron sulfides followed by
selective reduction. For example, at the
International Nickel Company in Sudbury,
pyrrhotite concentrate

21

SUMMARY

Leaching of Oxides,
Hydroxides,
and Complex Oxides

22

OXIDES & HYDROXIDES

z
z
z

Bauxite
Laterites
Copper, manganese, and uranium ores. A
minor amount of zinc occurs as oxide,
carbonate, and basic carbonate
A great part of zinc sulfide is first oxidized to
oxide which is then treated by wet methods.

Bauxite 1

23

Bauxite 2

Bauxite 3
Aluminum minerals in bauxite are soluble in
dilute H2SO4 but this process is not used on
large scale for the following reasons:
z

Iron minerals and to some extent titanium minerals are also soluble; this
will lead to an excessive reagent consumption and solution purification
problem later.
Al(OH)3 precipitated from acid solutions is gelatinous and difficult to
filter and wash.

Acid leaching is used only on a small scale to

produce aluminum sulfate needed for water
treatment.

24

Karl Josef Bayer (1847-1904)

Leaching of Bauxite

25

BAUXITE
Grushing

Bayer Process

Washing
NaOH
NaOH
make-up

Drying
Grinding

Leaching
Settling

Sand

Water
Dilution
Thickener

Red mud

Filtration

Red mud

Seed
Precipitation
Filtration

Washing

Calcination

Pure
Al 2O3

Evaporation
Centrifuge

Solid impurities

Recycle

Processing of Bauxite

26

Aluminate Solution

COPPER MINERALS

27

Processing of Copper Ores

Copper ores
SO2
Flotation

Sulfides

Smelting
Copper

H2SO4

Oxides
Leaching

Filtration

Bleed
solution

Residue

Recovery

Copper

Copper Oxide Ores

Acid Leaching
Copper ores
H2SO4
Leaching

Filtration

Residue

Solution
Cementation

Electrowinning

Cement
copper

Electrolytic
copper

Flotation
Sulfide
concentrate

28

Processing of Copper Oxide Ores

Oxidized ores

Oxidized ores
H2SO 4

H2SO 4

Leaching

Leaching
Sponge Fe

H2S

Precipitation
Float

Flotation
Solution
to
waste

Precipitation

Filtration

Flotation
Sink

Filtration

Filtration

Filtration

Gangue

Sulfide
concentrate

Solution
Cement copper
to
waste
and sulfide
concentrate

Gangue

Chalcopyrite ore
Crushing
and grinding
Bulk
flotation

Float

Chalcopyrite
Tailings

Steaming

SO2
MoS2

Selective
flotation

Leaching

Roasting

Dust
collector

Chalcopyrite
concentrate

Cu2+

MoO3

Re2O7

29

Copper- Cobalt Ores

Processing of Cu-Co ores

Copper-cobalt ore
H2SO4
Leaching

Filtration

Gangue

Electrowinning
Copper
Cobalt
recovery

Cobalt

30

Acid Leaching of

Copper Oxide Ores

Ammonia Leaching of Copper Oxide

Ores
Ore
2CuCO3 Cu(OH)2

NH4OH + (NH4)2CO3

Leaching
Residue

Recycle
Filtration

Distillation
Basic
carbonate

Water
NH3
CO2

Absorption

Calcination

CuO

31

Laterites 1

Manganese Ores

32

Processing of Manganese Ores

Manganese oxide
ore
Fe2+ or C

Reduction
H2SO4

MnO

H2SO4

H2SO3

Leaching

Leaching

Leaching

Filtration

Filtration

Filtration

MnSO4

MnSO4

MnSO4

Gangue

Gangue

Gangue

Manganese Nodules

33

Uranium Ores

Uranium Ores
Carbonate Leaching
Na2CO3 +
NaHCO3

Uranium ore
O2
Leaching
Filtration

Gangue

Precipitation
NaOH
Filtration
Calcination

Na2U2O7

34

Zinc Oxide

Leaching of ZnO
Zinc oxide calcine
ZnO fumes

Dilute Recycle
H2SO 4
Leaching

Reduction
(rotary kiln)
Filtration

Residue
Reduction
(blast furnace)

Slag
Fuming

Purification
Lead
Electrolysis

Pure zinc

35

Leaching of ZnO
The problem of ferrites

Zinc oxide calcine

Dilute H 2SO 4
recycle

Concentrated
H2SO 4

Leaching

Filtration

Residue

Purification

Electrolysis

Leaching 95 C

Gangue

Filtration

Iron
precipitation

Pure zinc
Filtration
Iron - containing residue

Zinc Oxide Leaching

Disposal of Residue

36

Complex Oxides
MINERALS

37

Pyrometallurgical method. Partial reduction with

anthracite in an electric furnace to get cast iron and
a slag rich in titanium. Titanium slag in mainly iron
magnesium titanate, (Fe,Mg)Ti4O10, and a small
amount of silicates
Hydrometallurgical method. Leaching of iron oxide
and obtaining a residue rich in titanium (9095%
TiO2) known as synthetic rutile.
The slag and synthetic rutile can then be processed
to TiO2 pigment or titanium metal.

Conc.
H2SO4

Ilmenite

Baking
H2O
Leaching

Leaching of Ilmenite

Filtration

4H+

FeTiO3 +

2+
2+
Fe + TiO + 2H2O

Residue

Crystallization
Centrifuge

FeSO4 4H2O
H2O

Seed
Hydrolysis
Filtration

Dilute
H2SO4

Drying
Calcination
TiO2

38

Titanium Raw Materials

Synthetic Rutile
FeTiO3 + 2H+ TiO2(impure) + Fe2+ + H2O

HCl

Ilmenite
Digestion
Filtration

Synthetic
rutile

Oxyhydrolysis
Fe2O3

39

Synthetic Rutile Plant

Western Australia

Oxyhydrolysis of FeCl2
2FeCl2 + 2H2O + O2
Fe2O3 + 4HCl

40

Conc.
H2SO4

Titanium
slag
Baking

Processing of
Titanium Slag

H2O
Leaching
Filtration

Residue
H2O

Seed
Hydrolysis
Filtration

Dilute
H2SO4

Drying
Calcination
TiO2

Chromite 1
z

Chromite is usually reduced in electric

furnace to make ferrochromium
For the production of high-purity chromium,
chromite is dissolved in acid then the
aqueous solution of pure chromium alum is
electrolyzed.

41

Chromite 2
FeCr2O4 + 8H+
Fe2+ + 2Cr3+ + 4H2O

Chromite 3

42

Niobium & Tantalum 1

Niobium & Tantalum 2

z

Columbite, tantalite, and pyrochlore are mainly used

to prepare ferroniobium and ferrotantalum by
pyrometallurgical methods
To prepare metallic niobium and tantalum a pure
oxide is usually prepared first by treating the
concentrates by hydrometallurgical methods
Tin slags, especially those from Malaysia and
Thailand, were at one time an important source of
niobium, tantalum, as well as tungsten.

43

Niobium & Tantalum 3

Wolframite and Scheelite 1

44

Wolframite and Scheelite 2

Acid digestion
Sulfuric should not be used

Wolframite and Scheelite 3

z

Alkaline Digestion

45

Leaching of Sulfides

46

Sulfides

Disulfides, S22
PYRITE, FeS2

47

Sulfide-Disulfide
COVELLITE, CuS

Arsenopyrite
z

FeAsS contains the diarsenide ion

As22

48

Thermal Properties

FeS + S
z FeAsS FeS + As
z CuI4Cu2II(S2)2S2 3CuI2S + 3S
z FeS2

Aqueous Behaviour
z

FeS2(s) ' Fe2+(aq) + S2 2(aq)

Cu4ICu2II(S2)2S2(s) '
4Cu+(aq) + 2Cu2+(aq) + 2S2 2(aq) + 2S2(aq)

2FeAsS(s) ' 2Fe2+(aq) + As22 (aq) + S22(aq)

49

Autooxidation of Disulfide Ion

z
z

S22 2S + 2e
S22 + 2e 2S2

Overall reaction:

S22 S + S2
Behaviour similar to peroxide ion
O22 O2 + 2e
z
O22 + 2e 2O2
Overall reaction:
z

2O22 O2 + 2O2
2H2O2 O2 + 2H2O

Potential pH Diagram
0.8

Oxidizing

0.4

HSO 4

SO 4
H2S

0.4

0.8

1.2
1

Reducing

E (Volts)

Elemental sulfur
0

HS

Acid
3

Basic
7

S2

11

pH

50

Apparent Anomalous
Behaviour
zCu2S
zNi3S2

Aqueous oxidation of Cu2S

Aqueous oxidation takes place in two steps
Cu2S + 2H+ + 1/2O2 CuS + Cu2+ + H2O
CuS + 2H+ + 1/2O2 Cu2+ + S + H2O

This sulfide behaves as if it were solid

solution of a metal and a sulfide
z

Cu2S behaves like Cu + CuS

Cu + 2H+ + 1/2O2 Cu2+ + H2O
CuS + 2H+ + 1/2O2 Cu2+ + S + H2O

51

Aqueous oxidation of Ni3S2

z

Ni3S2 + 2H+ + 1/2O2 2NiS + Ni2+ + H2O

NiS + 2H+ + 1/2O2 Ni2+ + S + H2O

Ni3S2 behaves like Ni + 2NiS

Ni+ 2H+ + 1/2O2 Ni2+ + H2O
NiS + 2H+ + 1/2O2 Ni2+ + S + H2O

Heating of Elemental Sulfur

Heated
Cooled

52

Viscosity of Elemental Sulfur

Viscosit y, poise

10 3

10 2

10

120

160

200

240

280

320

Temperature, C

53

Oxidation products of sulfides in

neutral or alkaline medium

54

Aqueous Oxidation of Sulfides

Franz von Soxhlet (1848-1926)

55

Industrial Applications 1
z

z
z

Falconbridge Process
Treatment of a mixture of Cu2S Ni3S2 obtained by smelting a copper
nickel sulfide concentrate
Ni3S2 + 6HCl 3NiCl2 + 2H2S + H2
Insoluble Cu2S is separated by filtration for copper recovery

Industrial Applications 2
Equity Silver Process
Copper concentrate is leached for 16 hours at
110C to solubilize arsenic and antimony
sulfides
z As2S3 + 3S2 2AsS33
z Sb2S3 + 3S2 2SbS33
After filtration, the copper concentrate is
shipped to smelters

56

Industrial Applications 3
z

Dissolution of nickel, cobalt, and copper

sulfides
MS + 2O2(aq) MSO4

Industrial Applications 4
z

Aqueous Oxidation of PbS-ZnS Concentrates

57

Industrial Applications 5
z

Aqueous oxidation of molybdenum sulfide in

water
Hydrolysis accompanies oxidation and as a result
molybdic acid is formed as a white precipitate:
z
z
z

MoS2 ' Mo4+ + 2S2

Mo4+ + 3H2O + 1/2O2 H2MoO4 + 4H+
S2 + 2O2 SO42

Industrial Applications 6
z

Aqueous oxidation of molybdenum sulfide in

alkaline medium

MoS2 ' Mo4+ + 2S2

z Mo4+ + 6OH- + 1/2O2 MoO42- + 3H2O
z S2 + 2O2 SO42
Overall reaction
MoS2 + 6OH + 9/2O2 MoO42 + 2SO42 + 3H2O
z

58

Industrial Applications 7
z

Sherritt-Gordon Process (now Dynatec):

Treating concentrates of copper, nickel, and
cobalt by ammonia to form soluble ammine
complexes
MS + nNH3 + 2O2 [M(NH3)n]2+ + SO42

Sherritt-Gordon Process
Ni-Co-Cu sulfide
Concentrate
Air

NH 3
Leaching
80 C. 700kPa

Residue: gangue
Fe (OH) 3, PbSO 4,
precious metals

Filtration

Boiling

Filtration

CuS

H 2S
Precipitation of
traces of Cu 2+
Filtration
Air

CuS, NiS, CoS

recycle to leaching
circuit

Oxidation

Filtration

Fe(OH) 3

Purified ammoniacal ammonium

sulfate solution containing
45g/L Ni and 1g/ L Co

59

Industrial Applications 8
Aqueous oxidation of Zinc sulfide
ZnS + 2H+ + 1/2O2 Zn2+ + S + H2O

Aqueous Oxidation of ZnS 1

Make up
H2SO 4
Sulfide
concentrate
O2
Leaching

Filtration

Gangue, S, PbSO 4
FeOOH

Purification
Spent
electrolyte

Electrolysis
Metal

60

Aqueous Oxidation of ZnS 2

Aqueous Oxidation of Pyrrhotite 1

z

In absencec of acid:
FeS + 2O2(aq) FeSO4(aq)

In presence of acid:
2FeS + 3/2O2(aq) Fe2O3 + 2S

61

Aqueous Oxidation of Pyrrhotite 2

Concentration

Concentration

Fe2+

Fe2+

Time

Time

Ferric Ion in Leaching 1

CuFeS2

FeCl3
Leaching

Filtration

S recovery

S0

Cyanidation

Au, Ag
recovery

Fe
Cementation
Cu

Filtration

Gangue and
pyrite

Crystallization

FeCl2 4H2O
Cl2

Fire refining

Oxidation

Copper

62

Ferric Ion in Leaching 2

PbS concentrate
FeCl3 + NaCl
Leaching

Hot filtration

S 0 + gangue

Crystallization
FeCl2 + NaCl
solution

Centrifuge
Lead chloride

Chlorine
Oxidation

Fused salt
electrolysis

Lead

Aqueous Oxidation of Pyrite 1

5

2+

[SO 4 ] / [Fe ]

3
2
1

2
pH

63

Aqueous Oxidation of Pyrite 2

FeS2 + 2H+ + 1/2O2 Fe2+ + H2O + 2S
z FeS2 + H2O + 7/2O2 Fe2+ + 2H+ + 2SO42
z Molar ratio [SO42]/[Fe2+] varies from 0 to 2
Mechanism
z FeS2(s) ' Fe2+(aq) + S22 (aq)
z Disulfide ion undergoes autooxidation
S22 S + S2
Overall reaction depends on leaching conditions
z

64

65