Week-3 and 4

1. Copper making video

[Link]

2. [Link]

3. Potash

4. Copper in our electrical world (to be seen later)

[Link]
ALTERNATIVE COMMINUTION TECHNOLOGIES

The Ideal Comminution Technology Crushing

depends on the product particle size
range to be obtained...
Rod Mills

AG/SAG Grinding – Single stage

SAG Grinding – Double stage

HPGR
Conventional Ball Milling

Vertical Mills

Isa Mills

1 10 100 1,000 10,000 100,000 1,000,000

Characteristic Product Particle Size Range, μm
Energy Efficiency
RANDOM vs. DIRECTED GRINDING MECHANISMS

DIRECTED CONTACTS

RANDOM CONTACTS
different grinding media of ball mills, rod mills and SAG mills

In typical Tumbling Mills, like Conventional Ball

Mills and SAG Mills, contacts between grinding
media (balls or rocks) and the particles to be
ground are essentially “chaotic”; hence very
inefficient in the conversion of supplied energy
into actual particle fragmentation.
Jaw crusher: Movable jaws Cone crusher: The cone shaft rotates
periodically reciprocate the jaws, around the fixed point at a week under
moving up and down. When the eccentric sleeve. Cone broken wall is
approaching, the material is crushed driven close to each other, and sometimes
by crushing, splitting, and impact the surface of the rolled wall fixed on the
between the two jaws. When leaving, adjusting sleeve can run off, so that the
the broken material is discharged ore is continuously subjected to
from the discharge port by gravity. impacting, pressing and bending in the
crushing chamber

Roller crusher: two round rollers are rotated in the opposite direction,
secondly, the roller crusher uses the friction of its surface to draw
materials into the crushing chamber, and materials are crushed. Then,
under the action of gravity, the finished product is discharged from the
gap between the two rollers.

Impact crusher
Aluminium Copper Iron Lead Tin Zinc Principal production routes for common metals

1. Pyrometallurgical methods including smelting, converting,

and fire refining are carried out at elevated or high
temperatures. A step called roasting or calcination may also be
incorporated in the flow sheet in the treatment of sulfide or
carbonate minerals.
2. Hydrometallurgical methods incorporate leaching of metal
values from the ores/minerals into aqueous solution. The
resultant solution is purified before precipitation of the metal
by pH and pO2 control, gaseous reduction, or cementation.
Roasting or calcination also forms an important step in the
treatment of sulfide and carbonate ores. In the production of
rare metals like uranium, thorium, zirconium and so on, the
leach liquor may be purified by fractional crystallization, ion
exchange, and/or solvent extraction techniques.
3. Electrometallurgical methods use electrical energy to
decompose the pure mineral that is present in aqueous
solutions or in a mixture of fused salts. If the metal is extracted
from the electrolyte using an insoluble anode the method is
called electrowinning. On the other hand if the impure metal (in
the form of the anode) is refined using a suitable electrolyte,
the method is known as electrorefining.
Principal minerals from which metals are extracted and other
metals which may be present in the same ore body

High grade metals and average concentrations in earth’s crust

The chemical equilibria for all of the
above reactions at any temperature
may be conveniently presented on
predominance diagrams, of logpSO2 or
logpS2 vs logpO2.
In this way, the ranges of sulphur and
oxygen pressures at any temperature
over which particular compounds are
stable may be readily identified.
✓ Rotary kilns were employed for the exothermic roasting of sulfidic
ores and for the endothermic removal of water of hydration and
carbon dioxide from fine-grained materials such as ores, phosphates,
alumina, ilmenite, and titanium dioxide.
✓ Today these processes are performed almost exclusively in fluidized-
bed reactors (→Fluidized-Bed Reactors), which offer better heat- and
mass-transport conditions.
✓ However, rotary kilns have advantages where softening, sticking, or
even partial melting of the material cannot be avoided
✓ In addition to common metals like copper, lead, zinc, and nickel several other
metals such as antimony, bismuth, cadmium, cobalt, mercury, and
molybdenum occur as sulfide minerals.
✓ Sulfides are not reduced with the most widely used reducing agents, carbon
and hydrogen, because the free energy change for the reactions 2MS + C =
2M + CS2 and MS + H2 =M+H2S is positive due to the lesser stability of CS2
and H2S, compared to most sulfides.
✓ Reduction of sulfides with metals is not economical. Furthermore, from most
sulfide minerals the metal value is not brought into aqueous solution by
leaching with common acids and alkalis.
✓ In the presence of an oxidant, chalcocite is leached quickly in dilute sulfuric
acid whereas bornite and covellite are leached slowly. Leaching is speeded up
in the presence of bacteria. But chalcopyrite, the major source of copper is
not leached.
✓ Under the circumstances, the only alternative seems to be the conversion of
sulfide concentrates into oxides by dead roasting, which can be easily
reduced with carbon (production of lead and zinc) or into mixed oxide and
sulfate by partial roasting and sintering, can be dissolved in dilute sulfuric
acid and the resultant solution is subjected to electrowinning (Zn extraction).
✓ Roasting of sulfides, in general, is exothermic and hence the temperature of the ore lump remains high enough for the
desired chemical reactions to occur fairly early during the roasting process. Every particle gets oxidized from the outside,
which leads to the formation of a case of solid product and leaves a core of unchanged zone
✓ In roasting, air in large amounts, sometimes enriched with oxygen, is brought into contact with the sulfide mineral
concentrate. This is done at elevated temperatures when oxygen combines with sulfur to form sulfur dioxide and with the
metal to form oxides, sulfates and so on. The oxidation must be done without melting the charge in order to prevent
reduction of particle surface–oxidizing gas contact area.
✓ Stirring of the charge in some manner also ensures exposure of all particle surfaces to the oxidizing gas. Exception to this
procedure is blast roasting-sintering, where the particle surfaces are partially melted and there is no stirring of the charge.
✓ The degree of sulfur elimination is controlled by regulating the air supply to the roaster and by the degree of affinity of the
mineral elements for sulfur or oxygen.
✓ For example, iron sulfide may all be oxidized because iron has more affinity for oxygen than for sulfur, while a copper mineral
in the same roaster feed will emerge in the calcine still as a sulfide due to greater affinity of copper for sulfur than for oxygen.
Roasting is essentially a surface reaction where the oxide layer is formed first and continues to remain as a porous layer
through which oxygen can pass into the still unreacted inner sulfide portion of the particle and the SO2 gas formed comes
out. Roasting is an exothermic reaction.
✓ This heat helps to keep the roaster at the required roasting temperature so that the process can continue with little extra
heat supplied by the burning fuel. Hence, sulfide roasting is an autogenous process, that is, where no extra fuel is supplied.
Copper is refined from ores in the ground, either through
underground or open-pit mines. Most of the copper ores mined
today are oxide or sulfide ores.
Processing of Copper Ores ✓ Copper is most commonly present in the earth’s crust as
copper iron sulfide and copper sulfide minerals, such as
Mining chalcopyrite (CuFeS2) and chalcocite (Cu2S).
✓ The concentration of these minerals in an ore body is low.
Transporting Typical copper ores contain from 0.5% Cu (open pit
mines, to 1 or 2% Cu (underground mines).
✓ Copper also occurs to a lesser extent in oxidized minerals
Primary Crushing Froth Floatation (carbonates, oxides, hydroxy-silicates, sulfates). Copper
Heap Leaching metal is usually produced from these minerals by
Thickening leaching, solvent extraction, and electrowinning. These
Oxide Ore: Sulfide Ore: processes are also used to treat chalcocite (Cu2S).
Solvent Extraction
Hydrometallurgy Pyrometallurgy ✓ A third major source of copper is scrap copper and copper
Smelting alloys. Production of copper from recycled used objects
Electrowinning is 10 or 15% of mine production. In addition, there is
Final Product: Electrolysis considerable re-melting/re-refining of scrap generated
99.99% pure copper
during fabrication and manufacture.
cathode

About 80% of the world’s copper-from-ore is produced by concentration/smelting/ refining of sulfide ores. The other 20% is
produced by heap leaching/solvent extraction/ electrowinning of oxide, and chalcocite ores. Copper production from recycled
end-of-use objects is about 15% of copper-from-ore copper production.
✓ The copper ores being mined are too lean in copper (0.5-2%
Cu) to be smelted directly.
✓ Heating and melting their huge quantity of waste rock would
require prohibitive amounts of hydrocarbon fuel.
✓ Fortunately, the CuFeS2 and Cu2S minerals in an ore can be
isolated by physical means into high-Cu concentrate, which
can then be smelted economically.
✓ The most effective method of isolating the Cu minerals is froth
flotation. This process causes the Cu minerals to become
selectively attached to air bubbles rising through a slurry of
finely ground ore in water.
✓ Selectivity of flotation is created by using reagents, which
make Cu minerals water repellent while leaving waste minerals
wetted.
✓ In turn, this water repellency causes Cu minerals to float on ➢ Reagents cause Cu-Fe sulfide and Cu sulfide minerals in the ore to
rising bubbles while the other minerals remain un-floated. attach to rising air bubbles, which are then collected in a short-lived
froth.
✓ The floated Cu-mineral particles overflow the flotation cell in a
➢ This froth is de-watered to become concentrate.
froth to become concentrate containing ~30% Cu. ➢ The un-floated waste passes through several cells before being
✓ Flotation is preceded by crushing and grinding the mined Cu discarded as a final tailing.
ore into small (~50 micron) particles. ➢ Many types and sizes (up to 300 m3) of cell are used.
✓ Its use has led to adoption of smelting processes which
efficiently smelt finely ground material.
Copper, and other non-reactive metals have a tremendous
advantage over reactive metals.
They can be processed as molten matte. Sulfur and iron may be
carried away by blasting an oxidizing stream through the matte,
which is the principle behind converting and related
technology.
Generally in extractive metallurgy, there is a technological
challenge to render the metal and its bonding elements
(sulphur, iron, oxygen, chlorine, etc.) sufficiently mobile to
permit separation.
Impu

✓ Roasting is not necessary in modern smelters that employ flash smelting; this entails a special furnace which allows the
roasting reactions to occur while the concentrate powder is falling through the feed chute. Roasting is still performed as
feed preparation for electric smelting, and certain antiquated smelting technologies.
✓ Smelting is succeeded by converting (usually Peirce-Smith) which eliminates iron and sulfur, and gives a crude form of
metallic copper, known as “blister copper”, or simply “blister”. It is roughly 99 wt%Cu with 1 wt%S. Blister copper is not
allowed to solidify, otherwise the residual sulfur is expelled from the cooling metal, resulting in SO2 blisters.
✓ To prevent the formation of blisters, the residual sulfur and oxygen is removed in the fire refining stage which immediately
follows the converting. The term “matte” does not apply to blister copper because it is predominantly metallic, as opposed
to sulfide.
✓ Fire refining furnaces are sometimes called anode furnaces, because they produce a copper that is sufficiently pure to be
cast into anodes (roughly 99.5 wt%Cu), that are then subject to electrorefining. The final cathode is roughly 99.99 wt%Cu
✓ In the matte smelting step, which takes place in a molten state, large portions
Copper of sulfur and iron contained in the copper mineral (typically chalcopyrite,
production mixed with some pyrite, FeS2, and other sulfides) are oxidized by oxygen-
enriched air.
flow sheet
✓ The modern trend is to increase the use of pure oxygen which decreases the
amount of nitrogen in the process streams and avoid the costs arising from
associated factors such as energy required to heat it and handling a larger
volume of gas. The sulfur dioxide is sent to the acid plant to be fixed as
sulfuric acid.
✓ The oxidized iron combines with silica, contained in the concentrate and added
as a flux, to form a fayalite slag (2FeOSiO2). The remaining metal sulfides
Cu2S and FeS, which are mutually soluble, form a copper matte of a certain
copper content, which varies from smelter to smelter (50–70%).
✓ The matte and the slag form an immiscible phase, enabling their separation,
with the lighter slag floating above the matte.
✓ Another important aspect of the mattemaking step, in addition to the removal
of iron and sulfur, is that large portions of undesirable impurities in the
concentrate such as As, Bi, Sb, and Pb are absorbed into the slag and thus
removed from copper.
✓ Valuable metals such as gold, silver, and other precious metals present in the
concentrate largely follow copper.

Copper matte converting process that involves complex gas–liquid–solid

multiphase flows is one of the key processes in copper pyrometallurgy
Direct Oxidation to Metal
This is a path from copper minerals directly to liquid copper in one overall step, a desire of copper-makers.
There are several problems to its use, as listed below:
1. The high degree of oxidation of iron and sulfur generates a large amount of heat, causing refractory problems and other
operating difficulties.
2. The high degree of oxidation of iron means a high magnetite concentration in the slag, even forming magnetite solids. This
makes the slag highly viscous.
3. Many harmful impurities, such as As, Bi, Sb, Pb, Se, and Te, return to copper from the slag phase.
4. At the higher oxygen partial pressure, the copper content in slag becomes high and the high viscosity of the slag increases the
copper physically entrained in it. Furthermore, with most of the iron being oxidized, the amount of slag also increases. All these
factors increase copper loss to slag, lowering the first-pass copper recovery.

Any metal production process that involves a molten stage is called “smelting.” Overall process of producing primary metals from
sulfide minerals by going through a molten stage.
The narrowest definition is the first step of the two-step oxidation of sulfur and iron from sulfide minerals, mainly Cu and Ni, i.e.,
matte smelting or matte making as opposed to converting in which the matte is further oxidized, in the case of copper making, to
produce metal

The reason for doing it in two stages is largely related to oxygen potentials in the two stages as well as heat production, the
former in turn affecting the slag chemistry (magnetite formation, for example) and impurity behavior.
If one goes all the way to metal in one step, much more of the impurities go into the metal, rather than the slag, and too much
heat is produced.
In the first stage, “matte smelting step,” as much iron, sulfur, and harmful impurities as possible are removed in slag, and the
matte is separated and treated in the converting step.
Matte Smelting Process

Suspension Smelting Bath smelting

S-Fe oxidation in molten bath

Flash smelting Cyclone smelting

• Gas Stream concentrate + flux cyclone reactor Few facts to remember

Sulphide mineral concentrate, together
• Gas solid interaction is high, wear
with slag component (SiO2-flux) is
injected with O2 enriched air

Furnace

Oxidation Heat release excessive

Autogenous reaction

Molten matte + slag droplets fall to bottom,

coalesce and separated in immiscible layers.
There are two basic types of flash furnaces: 1 ) the INCO process uses commercial oxygen and requires no external energy (i.e., is
autogenous); 2) the Outokumpu process uses preheated air or oxygen-enriched air.
The Outokumpu flash furnace can be autogenous if the air is enriched to ~ 40% oxygen; otherwise, it requires external fuel.
Major chemical reactions in the matte smelting step
• The sulfur dioxide concentration in the exhaust gas from a
reverbatory furnace is about 0.5–1.5%; that from an electric
furnace is about 2–4%. So-called flash smelting techniques have
therefore been developed that utilize the energy released during
oxidation of the sulfur in the ore.
• The flash techniques reduce the energy demand of produced
cathode copper. The SO2 concentration in the off gases from
flash furnaces is also higher, over 30%, and is less expensive to
convert to sulfuric acid
Major chemical reactions in the converting step
[Link]
Predominance area diagram
Lines describing equilibrium between any two condensed phases are given by
Thermodynamics of roasting equations:
Fig. 1

When roasting is carried out in air, pSO2 + pO2 =0.2 atm, the conditions
during roasting are as described by the dotted lines in Fig. 1. First, the
sulfide is roasted/converted into the oxide by reaction (5). Then the oxide
may be converted into sulfate.

Gibbs phase rule : P+F = C+2

C= no. of components = 3 (M, O, S)
F= degree of freedom
P= no. of phases = 5 (4 condensed phase and 1 gaseous)
If temperature is fixed and condensed phases
F = C-P
Gaseous phase: SO2, O2, SO3, S vapours
At any selected temperature the composition of the gas mixture is
defined by the partial pressures of two of the gaseous components.
Predominance area diagram
• Thermodynamic information on reactions in a system of three
components can be presented on a single graph using
predominance-area diagram or phase stability diagrams
• Diagrams facilitate the identification of a stable phase as function of
temperature and partial pressures of the participating gases.
• There are two main types of predominance-area diagrams:
(a) constant temperature and (b) variable temperature
Constant temperature:
• For the Cu–S–O system, for a temperature of 1000 K.
• At 1000 K, copper is seen to form only at very low pO2 , and thus it
cannot in practice be produced at this temperature.
• Suppose we have some Cu2S, chalcocite. The diagram says that at
1000 K one should be able to prepare metallic copper from it by
oxidizing with pure oxygen. However, the pressure needs to be
extremely low; otherwise, one will end up with CuO or Cu2O.

✓ When the sulfide CuS or Cu2S is oxidized by O2, a gas phase is formed.
✓ We first consider the cases of having one solid phase and the gas phase. Applying the phase rule P+F=C+2 (in which P denotes the number of
phases, F the degree of freedom, and C the number of components), P=2 in this case and there are three components, Cu, S, and O. Therefore, the
degrees of freedom become F=3. When temperature is fixed, one of these is used up.
✓ As sulfides react with oxygen, it is reasonable to choose the partial pressure of oxygen as one of them. The other could be partial pressure of sulfur.
✓ But as SO2 gas is the predominant gas species aside from oxygen, it is more convenient to select this. As equilibrium relations are linear in terms of
the logarithms of activities, predominance-area diagrams are drawn using log10pO2 and log10pSO2, with both partial pressures in units of atmosphere.
Variable Temperature Predominance-Area Diagrams

• Since there are three degrees of freedom and if oxidation

takes place at atmospheric pressure, one can fix that of
SO2 (= 1 atm)

• The figure indicates that liquid Cu is obtained above 1358 K, and

thus this would be the lowest temperature at which impurities in
the mineral could be removed by a slag through liquid–liquid
contact. The CuS phase hardly exists in the given temperature
range as shown in the figure, and the sulfate range is completely
absent.
• The liquid copper range spans about two orders of magnitude of
oxygen pressure, which means that it should be quite easy to
control process conditions to end in the liquid metal region.
Combined Cu–S–O and Fe–S–O System
• Chalcopyrite (CuFeS2) decomposes to Cu2S FeS liquid mixture
and S2 gas at 1 atm pressure at about 1250 K.
• Thus, the right-hand border of its stability region is the isotherm
for this temperature. Upon oxidizing FeS from chalcopyrite, the
probable product is Fe3O4.

• The region to the right is the liquid matte region, where the
Cu2S–FeS liquid is stable.
• This region is bordered on top by the line representing the
equilibrium of the following reaction:

• Above this, the stable phases are Cu2S and Fe3O4.

✓ Those that are more stable are shown below the less
stable ones, thus indicating which element can reduce
which sulfide when all the species are at their standard
states.
✓ They are shown for amounts of compounds containing
1/2S2 gas to allow direct comparison of the stability of
the various compounds.
✓ It is seen that no inexpensive elements except oxygen
are available to remove sulfur from sulfides. Thus, the
typical process to remove sulfur from sulfide minerals
starts with oxidation to form SO2 and SO3.

Ellingham diagram for sulfides (per 1/2S2 gas).