HYDROMETALLURGY

2 Leaching mechanisms

Fathi Habashi
Department of Mining, Metallurgical, and Materials Engineering

Laval University, Quebec City,,Canada

Fathi.Habashi@arul.ulaval.ca

Hydrometallurgy
Oxidant

Ore

Leaching agent

Leaching

Solid-Liquid
Separation

Solidto waste

Solution
Concentration
Purification

Precipitant
or electric
current

Precipitation

Pure
Metals
compounds

LEACHING 1
Leaching Agents
Solubility. Large and rapid solubility of the material to be leached in
the leaching agent.
Cost. An expensive reagent is undesirable because any traces lost
during handling will represent a large economic loss.
Materials of construction. If the leaching agent is corrosive and has
to be handled in tanks made of stainless steel, titanium, or
Hastalloy, the capital cost will be high, and therefore its use will be
less desirable.
Selectivity. An ideal reagent will extract only the desired component.
Regeneration. Ability of regenerating the reagent for recycle is also
an important criteria

LEACHING 2

LEACHING 3
Bases such as NaOH or NH4OH are more
expensive than H2SO4 but they are used
because of the following advantages:
Negligible corrosion problems.
More selective, i.e., suitable for ores containing much
gangue which reacts with acids but not with the
bases. Examples of such gangue minerals are
limestone, dolomite, iron oxide, iron carbonate, etc.

LEACHING 4

LEACHING 4
An oxidizing or a reducing agent is sometimes
needed during leaching to solubilize certain
minerals which do not dissolve otherwise. For
example, during leaching of gold, sulfide
minerals, uranium ores, etc.
Commonly used oxidizing agents are: oxygen
(or air), ozone, hydrogen peroxide, ferric ion,
manganese dioxide, sodium nitrate, and sodium
chlorate
Commonly used reducing agents are ferrous ion,
and sulfur dioxide.

LEACHING 5

Hydrometallurgical
Reactions

Physical processes
Chemical processes
Electrochemical processes
Electrolytic processes

Physical Processes
Hydration
Na+Cl(s) + (n +m)H2O Na(H2O)+n(aq)+ Cl(H2O)m(aq)

Speed of agitation
Temperature

Chemical Processes

Ionic-covalent solids
Covalent solids

Chemical Processes

Ionic-covalent
solids

Chemical Processes

Ionic-covalent
Neutralization
Complex formation
solids

Dispalcement
Oxidation
Protonation

Chemical Processes. Ionic-covalent solids

Neutralization

Chemical Processes. Ionic-covalent solids

Neutralization

Chemical Processes. Ionic-covalent solids

Complex formation

Dissolution of lead sulfate in sodium chloride solution. Lead

sulfate has a low solubility in water:

PbSO4(s) Pb2+(aq) + SO42 (aq)

In presence of chloride ions, the chloroplumbate ion is formed:

Pb2+ + 4Cl [PbCl4]2

thus decreasing considerably the concentration of Pb2+ ion. This disrupts
the equilibrium of Pb2+ in contact with the solid phase, PbSO4, thus more
solid goes into solution. Overall reaction :

PbSO4 + 4Cl [PbCl4]2 + SO42

Chemical Processes. Ionic-covalent solids

Complex formation

The dissolution of HgS in a solution of

sodium sulfide can be represented
similarly:
HgS(s) Hg2+ + S2(aq)
Hg2+ + 2S2 [HgS2]2

Chemical Processes. Ionic-covalent solids

Displacement 1

The dissolution of a sulfide in a solution

containing a metal ion that forms a less
soluble sulfide is a displacement
reaction. For example, the dissolution of
ZnS in CuSO4 solution

Displacement 2

Chemical Processes. Ionic-covalent solids

Oxidation

The dissolution of sulfides in oxygenated

water. For
example, the aqueous oxidation
of FeS to ferrous sulfate:
FeS(s) Fe2+(aq) + S2(aq)
S2 + 2O2 SO42
Overall reaction:
FeS(s) + 2O2(aq) Fe2+ + SO42
Oxygen shares electrons with the sulfide ion

Chemical Processes. Ionic-covalent solids

Protonation 1

Protonation reactions involve the dissolution

of compounds of weak acids in strong acids,
or formation of volatile acids.

Protonation 2
For example dissolution of CaCO3 in acids:
CaCO3(s) Ca2+(aq) + CO32(aq)
CO32 + H+ HCO3
HCO3 + H+ H2CO3
H2CO3 H2O + CO2
The overall reaction:
CaCO3 + 2H+ Ca2+ + CO2 + H2O

Chemical Processes

covalent solids
Covalent bond, e.g., that between silicon and
oxygen in silica and the silicates, is a strong
bond that cannot be broken easily by aqueous
solutions
The strong SiO bond in silica is not solubilized by
boiling with concentrated acids except hydrofluoric
because of the formation of SiF4 which is a gas that
may volatilize or react with water to form
fluorosilicic acid, H2SiF6.

Electrochemical Processes
1
The solid is a conductor, e.g., a metal, or a solid with
partially ionic and partially covalent bonds that possesses
semiconducting properties, e.g., UO2, ZnS, and CuFeS2.
There is a transfer of electrons from the solid phase or from
solution to the reacting species, i.e., the process involves
an oxidationreduction couple. The ions or molecules in
solution simply diffuse through the boundary layer to meet
the solid surface to pick up or give away electrons.
The solid dissolves at certain localized points while the
electron transfer takes place at other points usually much
further.
The oxidation and the reduction reactions proceed
simultaneously.

Electrochemical Processes
2
The kinetics of these reactions are
influenced by the presence of lattice
defects in the solid and/or the presence of
trace impurity which may increase or
decrease the electrical conductivity of the
solid, and hence the availability of the
electrons.
The rate of dissolution increases with
increased reagent concentration and with
increased temperature. When two
reagents are present, the rate depends
only on one reagent at a time.

Electrochemical Processes

Metals in oxygenated water

Metals in dilute acid
Metals by displacement
Metal with complex formation
* Oxides
* Sulfides

ELECTROLYTIC PROCESSES
An outside potential (EMF) is imposed on
the solid which is made as anode in an
electrolytic cell to cause its dissolution.
For a metal: M Mn+ + neFor a semiconducting divalent sulfide: MS
M2+ + S + 2e

SUMMARY

Kinetics of
Hydrometallurgical Reactions
Theory

of diffusion introduced by the

German physicist Adolf Fick in 1855
The concept of the boundary layer
introduced by the German chemist
Walther Nernst in 1904

Diffusion

Diffusion is the tendency of

any substance to spread
uniformly throughout the
space available to it. It is a
result of molecular movement

Fick's Law

dn
dC
= -D A
dt
dX

THE BOUNDARY LAYER

THE BOUNDARY LAYER

When a solid C is agitated in water and the solution is
analyzed at intervals, it will be found that the rate of
increase of the solute concentration follows the equation

d[C]
= k [C]s [C]
dt

dn D A

=
[C ] s [C ]
dt

THE BOUNDARY LAYER

Concentration

n
[C ] =
V

d [C ] D A

[C ] s [C ]
dt
V

Rate Determining Step

Diffusioncontrolled
processes
Chemicallycontrolled
processes

Characteristics of Hydrometallurgical Reactions

Effect of fluid
velocity

D
Rate =
A[C ]

Characteristics of Hydrometallurgical
Reactions
Effect

of temperature

D =

RT 1
N 2 r

k = A e-E/RT

Change of Mechanism

Effect of concentration
Dissolution of CuO in sulfuric acid

Change
oftemperature
Mechanism
Effect of
Reaction: Pd2+ + Cu Pd + Cu2+

SUMMARY
Diffusion of reacting species to the
interface
Adsorption at the interface
Reaction at the interface
Desorption of the products
Diffusion of the products from the interface

SUMMARY
Diffusion-controlled processes
Chemically controlled processes
Intermediate-control processes

THANKS