Unit operations

of metals production

Contents

Unit operations of Mining and enrichment

Pyrometallurgical unit operations

Hydrometallurgical unit operations
Electrochemical unit operations

Not included
in this presentation

Casting processes
Thermo-mechanical treatment of metals
Metal product manufacture

Metallurgy:
introduction

Mining &
Enrichment

Properties of
metals
Physical
metallurgy
Hot and cold
rolling
(...)

Material
sciences
Extractive
metallurgy

Electrometallurgy

Thermodynamics
Reaction
kinetics

Hydrometallurgy

Pyrometallurgy

Ores
Mining
Enrichment
Crushing
Screening
Mechanical
separation
(...)

Theory

Pyrometall.
pretreatment

e.g. Roasting

Water

Iron and
steel
Sulphideores (e.g. Cu)

(...)

Impurity
removal

Leaching

Methods

Transport
phenomena

Hydrometallurgical
metal production

Metal
recovery

Similar
methods

Solvents

Mass
transfer
Heat
transfer
Fluid
dynamics

e.g.
zinc
nickel

Electrowinning
Cementation

Acidic

Basic

Organic

Sintering
Coking
Flash
smelting

Chemical
precipitation

Blast
furnace
Converters
(PS)

Solvent
Ion
extraction
exchange

Sulphur
removal

Converters
(LD/AOD/...)
Electric
furnaces

Casting
Ladle
treatments
Pyrometallurgical
metal production

e.g.
iron/steel
copper

How to choose a process?

Transport
Energy
Raw materials

Water needed

Markets

Production chain

Pyromet. unit operations

Hydromet. unit operations
Electro-chem. unit operations

$
Products

Residues

Pyrometallurgical
unit operations
Production of metals

Raw materials

Drying

Products

Raw material
pretreatments

Metal
extraction

Metal
refining

Thermal pretreatment

Reduction
and oxidizing

Metal
raffination

Sintering
Pelletizing
Calcination

Coking

Roasting

Reduction Matte
of oxides production

Temperature
control
Composition
control

Impurity removal

Drying

Dangerous to charge wet materials to the high

temperature processes
The moisture that is allowed depends on the further
processing

Mechanical moisture removal prefered

Thermal drying requires a lot of energy

Counter-current drum-driers are common in the

drying of metallurgical raw materials
Utilisation of the process waste heat streams

Sintering

Problems in processing fine materials

Gas permeability
Dusting

Thermal agglomeration
Partial melting
Minimisation of the surface energy
as a driving force for agglomeration

Chemical and mineralogical changes in material

Drum-, batch- or belt-sintering
Pretreatment: Micropelletising

Pelletizing

Feeding of concentrates, binding materials and water

into the rotating and sloped pelletising drum or plate
Capillar forces caused by moisture as cohesive force
Aftertreatments in order to achieve wanted
properties
Sintering
Shaft furnace

Small pellets are fed back

to the process

Calcination

Thermal disintegration of a compound (which leads

into a formation of gaseous product)
Thermal conductivity (endothermic reactions)
Removal of gas from the reaction surface

e.g. calcination of limestone to produce burned lime

Use of lime in iron and steelmaking slags
CaCO3 = CaO + CO2
HR >> 0
Counter-current shaft furnace or rotating drum

Other examples
Disintegration of CaMg(CO2)2 or Al(OH)2

Coking

Pyrolysis of coal in order to modify it to be more

suitable for metallurgical processes
Removal of water and volatile components
Agglomeration of coal particles
Porous coke as a result

Dry or wet quenching

Several by-products
Reducing gas (H2, CO)
Raw materials for chem. industry

Roasting

A process in which an anion of a solid compound is

changed without changing the valency of the cation
High temperature processing of the sulphide ores
without agglomeration
Often used as a pretreatment for the hydrometallurgical
processes

Examples
Oxidising roasting
Sulphating roasting
Chlorine/Fluor/Alkalines/...

Oxidising roasting

Difficulties to reduce sulphide ores using carbon

e.g. 2 ZnS + C = 2 Zn + CS2 or ZnS + CO = Zn + COS
Equilibrium is strongly on the reactants side

Roasting of sulphides into the oxides

MeS + 3/2 O2 = MeO + SO2
Used e.g. in the production of lead, copper, zinc, cobalt,
nickel and iron when using sulphide ores as raw materials
SO2 SO3 H2SO4

Fluidized bed, sintering or shaft furnace roasting

Products are either fine material or porous agglomerates

Sulphating roasting

Used in separation of metals from complex materials

Some metals react to sulphates that are soluble to water

MeS + 3/2 O2 = MeO + SO2

SO2 + 1/2 O2 = SO3
MeO + SO3 = MeSO4

Some are left as oxides (non-soluble)

A pretreatment for hydrometallurgical processes

Usually fluidized bed roasting
Often used to remove iron from more valuable
metals (Cu, Ni, Zn, Co)
When T > 600 C Ferrisulphate is not stable

Reduction of oxides

MeO + R = Me + RO
Me is a metal
R is a reducing
component (an element
or a compound which
forms an oxide which is
more stable than MeO
in the considered
temperature)

Reduction of oxides

Carbo-thermal reduction
MeO + C = Me + CO
In practice:

MeO + CO = Me + CO2
C + CO2 = 2 CO (= Boudouard reaction)

Metallothermal reduction
MeO + M = Me + MO

Gas reduction
Usually H2 and CO (separately or as a mixture)

MeO + H2 = Me + H2O
MeO + CO = Me + CO2

Reduction of oxides
Specific and total CO2-emissions
of the Finnish steel industry
The largest industrial CO2-emissions
in Finland and Sweden (Mt)

Matte production

Separation of metals from the sulphides

Worthless metal is oxidised Oxidic slag
Wanted metal is still as a sulphide Matte

Matte is further refined Metal

Used e.g. in the production of copper, nickel and
lead
2 CuS + O2 = Cu2S + SO2
FeS2 + O2 = FeS + SO2
2 FeS + 3 O2 + SiO2 = Fe2SiO4 + 2 SO2

Removal of impurities
(from iron/steel)

Carbon removal (hot metal crude steel)

To achieve wanted properties
Decarburization in BOF-converters

Removal of other oxidising impurities/elements (Si, Mn, P)

Oxygen blowing Oxide formation Slag/Gases
Temperature is increased
Scrap melting

Vacuum treatment

Burning of carbon is more efficient

in lowered pressure
Partial pressure of CO can also be
lowered using inert gases

Removal of impurities
(from iron/steel)

Deoksidation / Oxygen removal

Solubility of oxygen in steel melt is appr. 0,2 % (T > 1500 C)
Solubility decreases when temperature is decreased

Causes CO formation, oxidation of alloying elements, etc.

Alloying, diffusion or vacuum deoxidation

Gas removal
Solubilities of gases decrease when T is decreased (cf. O)
Gas removal is based on decreasing the partial pressure of the
concerned element in the gas phase (vacuum, inert gas)

Sulphur removal
Formation of CaS Into the slag

Composition control
(Steel)

Alloying of steel is made mainly in the BOF-converters

after the blowing
More accurate alloying in the steel ladle
Lumps
Powder injection
Wire injection

Stirring
Inductive
Using an inert gas

Temperature control

Increased significance due to continuous casting

Optimisation of a tap temperature
Inductive heating
Use of fuels
Plasma heaters
Chemical heating (Al, Si)
Electric arcs
Insulation
Scrap cooling
Stirring

Hydrometallurgical
unit operations
Byproducts

Wastes

Raw material

Impure
raw
materials Poor
raw
materials

HydroPyrometallurgical metallurgical

Activation

Leaching
Impurity
removal

Cleaning /
regeneration of
the solvent

Metal
recovery
Electrochemical

Chemical

Waste
By-product
Waste
treatment

Product

Leaching

Grinding, enrichment and activation as pre-treatments

Solvents
Water

For sulphates and chlorides

Acids

Sulphuric acid most commonly used

Nitric and hydrochloric acids
more expensive and corroding

Bases

Ammonia water

Organic solvents

Leaching

Direct leaching
For poor ores and residues

Tank leaching (in atmospheric pressure)

For rich ores and concentrates
Smaller reactors and faster processes
Stirring

Autoclave leaching
Tank leaching in which reaction kinetics are enhanced by
increasing temperature over the boiling point of the solution
(in increased pressure)

Metal recovery

Crystallization

Separation of solid crystal from a homogenic solution

Pure products (impurities only on the surfaces)
Saturated solution
Kinetics?

Chemical precipitation (as sulphides or as metals)

Addition of anions or cations in order to form a compound
with a low solubility
Selectivity
Gases (H2S, H2, SO2, CO) are efficient additives

Electrowinning

Impurity removal

Procedures between leaching and metal recovery

Physical removal of solid materials
Thickening
Filtering

Removal of impurities from the solution

Similar methods as in metal recovery
Ion exchange
Liquid-liquid-extraction

Ion exchange

To remove small amounts of impurities from large

amounts of solutions
Best with dilute solutions (< 10 ppm)

Possibility to achieve very low impurity levels

Resin to which metal ions are tranfered from
solution
Selectivity

Saturated resin is recovered with other solutions

to which the metal ions are transfered
Saturation of metals as chlorides, sulphates, etc.

Liquid-liquid-extraction

Recovery of metal ions from the water solution

using an organic extraction agent
Two immiscible liquids

Reaction area is increased using efficient stirring

Formation of complex compounds

Settling in order to separate two liquid phases
Recovery of valued metals from the complex compounds

Selectivity

Cementation

Substitution of a metal ion (M+) with a less noble

metal (Me)
Me(s) + M+(aq) = Me+(aq) + M(s)

Efficiency depends on the difference of the

nobilities of the metals

Electro-chemical
unit operations

Electrolysis = reduction/oxidation that is controlled

with the electricity
Electrolyte that contains ions
Anions (-) are transfered to the anode (+) Oxidation
Cations (+) are transfered to the cathode (-) Reduction

Can be hydrometallurgical ...

Electrowinning
Electrolytical refining

... or pyrometallurgical
Molten salt -electrolysis

Electrowinning

Anodes are not dissolved (e.g. Pb)

Formation of oxygen as a main reaction
Formation of hydrogen occurs with less noble metals
The amount of H+-ions is increased in the electrolyte

Metal-ions from the solution are precipitated in the

cathode
The amount of metal ions is decreased in the electrolyte
Metal-poor electrolyte is recycled back to the leaching
process

Used in the production of nickel and zinc

Electrolytical refining

Anodes are dissolving (impure metal to be refined)

Wanted metal is dissolved to the electrolyte
All the less noble metals are also dissolved
More noble metals dont dissolve an anode sludge is
formed

Cathodes
Precipitation of a wanted metal
Less noble metals are left in the electrolyte from which they
can be recovered

Refining of pyrometallurgically produced metals

Especially copper

Electrolysis using molten

salts as electrolytes

Halide melts as electrolytes

The principle is same as in hydrometallurgical electrolyses
Higher temperatures
Refractoriness of the reactors etc.

Used in the production of aluminium, magnesium,

beryllium, cerium, lithium, potassium and calcium
i.e. metals that are produced from the raw materials with
high melting temperatures