Escolar Documentos
Profissional Documentos
Cultura Documentos
Extraction Metallurgy
Part 2: Case studies
Copper Pyrometallurgy route and environmental concerns.
The hydrometallurgical alternative.
Hydrometallurgical processes ion exchange processes,
solvent extraction, and bacterial leaching.
Iron Pyrometallurgy and the blast furnace.
Silicon The electric arc furnace. Purification by the
Czochralski process.
Pyrometallurgy of copper
Reminder: Pyrometallurgy is the use of heat to reduce
the mineral to the free metal, and usually
involves 4 main steps:
1. Calcination: thermal decomposition of the ore with
associated elimination of a volatile product.
Pyrometallurgy of copper
Cu ore usually associated with sulphide minerals.
Most common source of Cu ore is the mineral
chalcopyrite (CuFeS2), which accounts for 50% of Cu
production.
Other important ores include:
chalcocite [Cu2S],
malachite [CuCO3 Cu(OH)2],
azurite [2CuCO3 Cu(OH)2],
bornite (3Cu2S Fe2S3),
covellite (CuS).
Pyrometallurgy of copper
The following steps are involved in Cu extraction:
1. Concentration
2. Roasting
3. Smelting
4. Conversion
5. Refining
Pyrometallurgy of copper
1. Concentration
Only ~0.7% of the extracted ore contains Cu
Finely crushed ore concentrated by the froth-flotation
process:
Copper ore slurry mixed with:
Pyrometallurgy of copper
S
1. Concentration (cont.)
R
S
Na3PS2O 2
S
R1
H
N
R2
Hydrophobic attracted
to hydrocarbon pine oil
Hydrophilic attracted
to sulphide minerals
CH3
S
K
H3C
Potassium
amyl xanthate
Pyrometallurgy of copper
1. Concentration (cont.)
Raising the pH causes the polar ends to ionize more,
thereby preferentially sticking to chalcopyrite (CuFeS2)
and leaving pyrite (FeS2) alone.
Air is bubbled through the suspension.
Finely divided hydrophobic ore particles latch on to the
air bubbles and travel to the surface where a froth is
formed.
The froth containing the Cu ore is skimmed off and
reprocessed.
Pyrometallurgy of copper
1. Concentration (cont.)
In this manner, the ore is
concentrated to an eventual
value of over 28% Cu.
The remaining material (sand
particles & other impurities) sink
to the bottom & is discarded or
reprocessed to extract other
elements.
Pyrometallurgy of copper
1. Concentration (cont.)
Froth-flotation
Pyrometallurgy of copper
2. Roasting
Involves partial oxidation of the sulphide mineral with
air at between 500 C and 700 C.
For chalcopyrite, the main reactions are:
CuFeS2(s) + 4O2(g) CuSO4(s) + FeSO4(s)
4CuFeS2(s) + 13O2(g) 4CuO(s) + 2Fe2O3(s) + 8SO2(g)
Reactions are exothermic, roasting is an autogenous
process requiring little or no additional fuel.
NB, not all the sulphides are oxidised, only around 1/3.
Rest remain as sulphide minerals.
Pyrometallurgy of copper
2. Roasting (cont.)
Objectives of roasting:
1)
2)
3)
Pyrometallurgy of copper
3. Smelting
Smelting consists of melting the roasted concentrate
to form 2 molten phases:
1) a sulphide matte, which contains the iron-copper
sulphide mixture.
2) an oxide slag, which is insoluble in the matte, and
contains iron oxides, silicates, and other impurities.
Smelting is carried out at around 1200 C, usually with a
silica flux to make the slag more fluid.
The matte layer sinks to the bottom, and the slag layer
floats on top of the matte & is tapped off & disposed of.
Pyrometallurgy of copper
3. Smelting (cont.)
The main reaction is the reduction of copper oxides
(formed during roasting) back into copper sulphide to
ensure that they migrate into the matte phase:
Pyrometallurgy of copper
4. Conversion
After smelting, matte contains from between 30 to
80% Cu in the form of copper sulphide.
The sulphur is removed by selective oxidation of the
matte with O2 to produce SO2 from S, but leave Cu
metal.
Converting is carried out in two stages: 1) an iron
removal stage, and 2) a copper-making stage.
Pyrometallurgy of copper
4. Conversion (cont.)
Iron removal
A silica flux is added to keep the slag (see below)
molten.
Pyrometallurgy of copper
4. Conversion (cont.)
Copper making
The sulphur in the Cu2S can now be oxidized to
leave behind metallic copper according to the
following reaction:
Cu2S(l) + O2(g) 2Cu(l) + SO2(g)
The end product is around
98.5% pure & is known as
blister copper because of
the broken surface
created by the escape of
SO2 gas.
Pyrometallurgy of copper
5. Refining
Almost all copper is refined by electrolysis.
The anodes (cast from blister copper) are placed into
an aqueous CuSO4/H2SO4 solution.
Thin sheets of highly pure Cu serve as the cathodes.
Application of a suitable voltage causes oxidation of
Cu metal at the anode.
Cu2+ ions migrate through the electrolyte to the
cathode, where Cu metal plates out.
Pyrometallurgy of copper
5. Refining (cont.)
Metallic impurities more active then Cu are oxidized at
the anode, but dont plate out at the cathode.
Less active metals are not oxidized at the anode, but
collect at the bottom of the cell as a sludge.
The redox reactions are:
Cu(s)
Cu2+(aq) + 2eCu2+(aq) + 2eCu(s) E red = -0.83V
Pyrometallurgy of copper
5. Refining (cont.)
Pyrometallurgy of copper
Environmental impact
Large amount of gases produced present air pollution
problems, in particular SO2 gas
acid rain.
Dust produced contains heavy metals such as
mercury, lead, cadmium, zinc
health problems.
Waste water contaminated with:
Insoluble substances, mostly waste sludge (finely ground rock).
Soluble substances (heavy metals, sulphates).
Chemicals from flotation process.
Pyrometallurgy of copper
Environmental impact
Hydrometallurgy of copper
Advantages
Much more environmentally friendly than
pyrometallurgy.
Compared to pyrometallurgy, only a fraction of the
gases liberated into the atmosphere.
Emissions of solid particles comparatively nonexistent.
Disadvantages
Large amount of water used,
contamination.
Hydrometallurgy of copper
The following steps are involved:
1. Ore preparation
2. Leaching
3. Solution purification
4. Metal recovery
Hydrometallurgy of copper
1. Ore preparation
Ore undergoes some degree of comminution
(crushing & pulverisation) to expose the Cu oxides &
sulphides to leaching solution.
Hydrometallurgy of copper
1. Ore preparation (cont.)
Amount of comminution depends on quality of ore:
Higher grade ore more comminution.
Lower grade ore less comminution.
(Why??)
Hydrometallurgy of copper
2. Leaching
Definition : The dissolution of a mineral in a solvent, while
leaving the gangue (rock or mineral matter of no value)
behind as undissolved solids.
Hydrometallurgy of copper
2. Leaching (cont.) (a) Dump leaching
Hydrometallurgy of copper
2. Leaching (cont.) (b) Heap leaching
Similar to dump leaching except ore not simply dumped on a
hillside, but is crushed to gravel size & piled onto an artificial
pad.
After leaching (6 months to 1 year) gangue is removed from
pad, disposed of & replaced with fresh ore.
Hydrometallurgy of copper
2. Leaching (cont.)
Leaching reactions
Nature of ore determines if leaching is non-oxidative or
oxidative.
Non-oxidative leaching: No change in oxidation state.
e.g. (1) dissolution of copper sulphate by water:
CuSO4(s) + H2O(l)
Cu2+(aq) + SO42-(aq)
Hydrometallurgy of copper
2. Leaching (cont.)
Oxidative leaching: Many ores only soluble once oxidised.
e.g. covellite (CuS) much more soluble if oxidised to CuSO4
CuS(s) + O2(g)
CuSO4(aq)
CLASS EXERCISE : work out which species is oxidised,
and which is reduced, and write out the balanced half
reactions for each.
SOLUTION: CuS
O2
CuSO4
Cu = +2, S = -2
O=0
Cu = +2, O4 = -8, S = +6
S-2
S+6 + 8e(oxidation)
2O2 + 8e4O2- (reduction)
Hydrometallurgy of copper
2. Leaching (cont.) (c) Bacterial leaching
Several bacteria, especially Thiobacilli, are able to
solubilise metal minerals by oxidising ferrous to ferric
iron, as well as elemental sulphur, sulphide, and other
sulphur compounds to sulphate or sulphuric acid.
20 to 25% of copper produced in the USA, and 5% of
the worlds copper is obtained by bacterial leaching.
Very slow process; takes years for good recovery
But low investment and operating costs.
Hydrometallurgy of copper
2. Leaching (cont.) (c) Bacterial leaching
Thiobacilli
Hydrometallurgy of copper
2. Leaching (cont.) (c) Bacterial leaching
Mechanisms
M2+ + SO42-
Hydrometallurgy of copper
2. Leaching (cont.) (c) Bacterial leaching
Mechanisms: Indirect
2Fe2(SO4)3 + 2H2O
Fe
Fe3+ (ferric)
Hydrometallurgy of copper
2. Leaching (cont.) (c) Bacterial leaching
Mechanisms: Indirect
4Fe2+
4Fe3+ + 4e- (oxidation)
O2 + 4e2O2(reduction)
CuFeS2 + 2Fe2(SO4)3
CuSO4 + 5FeSO4 + 2S
Hydrometallurgy of copper
2. Leaching (cont.) (c) Bacterial leaching
Mechanisms: Indirect
Hydrometallurgy of copper
2. Leaching (cont.) (c) Bacterial leaching
Mechanisms: Direct
CuSO4
Hydrometallurgy of copper
2. Leaching (cont.) (c) Bacterial leaching
Compared to other extraction techniques:
Hydrometallurgy of copper
2. Leaching (cont.) (c) Bacterial leaching
Compared to other extraction techniques:
ADVANTAGES:
Economical: Simpler, cheaper, less infrastructure.
More environmentally friendly; no SO2 emissions, less
landscape damage.
DISADVANTAGES:
Economical: Very slow compared to smelting; less
profit. Delay in cash flow for new plants.
Environmental; Toxic chemicals sometimes produced.
H2SO4 pollution. Precipitation of heavy ions (Fe, Zn,
As) pollution.
Hydrometallurgy of copper
3. Solution Purification
Leaching reactions not perfectly selective other
elements in solution as well, not just Cu. These need
to be removed.
Hydrometallurgy of copper
3. Solution Purification
Ion exchange chromatography
DEFINITION: a solution containing a mixture of metal
ions is contacted with a resin that is insoluble in the
metal-ion solution.
Ion-exchange resin consists of an inert solid phase to
which labile functional groups are chemically bonded.
Functional groups can either be acidic (H+) or basic
(OH) groups that exchange with cations (M+) or
anions (M), respectively.
The ion-exchange process is reversible.
Hydrometallurgy of copper
3. Solution Purification
Ion exchange chromatography: Theory
Analyte molecules retained on a column (stationary
phase) based on coulombic (ionic) interactions.
Stationary phase has ionic functional groups (R-X)
that interact with analyte ions of opposite charge.
Two types: cation exchange chromatography:
R-XC+ + M+BR-XM+ + C+Banion exchange chromatography:
R-X+A- + M+BR-X+B- + M+A-
Hydrometallurgy of copper
3. Solution Purification
Cu Ion exchange chromatography
Hydrometallurgy of copper
3. Solution Purification: Solvent extraction
DEFINITION: a method to separate compounds
based on their relative solubilities in 2 different
immiscible liquids.
In industry, this is usually set up as a continuous
process.
Hydrometallurgy of copper
3. Solution Purification: Solvent extraction
Hydrometallurgy of copper
3. Solution Purification: Solvent extraction
Organic + aqueous stream pumped into a mixer.
Organic (containing an extractant) and aqueous
components mix, and ion transfer occurs between them.
Once ion transfer is complete (equilibrium), mixture is
allowed to separate.
Aqueous solution is removed & the organic phase
(containing the Cu2+) is mixed with an aqueous stripping
solution.
Cu2+ moves back into the aqueous phase, and the two
phases are again allowed to separate.
The aqueous phase (containing the Cu2+) is removed &
the organic phase is recycled back into the first mixer.
Hydrometallurgy of copper
3. Solution Purification: Solvent extraction
Extractants
The most successful extractants for copper (II) are of the
ortho-hydroxyoxime type:
OH
OH
R = alkyl ,phenyl, or H
R
R1 = alkyl
Hydrometallurgy of copper
3. Solution Purification: Solvent extraction
Extractants
At low pH (1.5 2.0) the ortho-hydroxyoxime extractant
complexes the Cu(II).
During back-extraction (stripping stage) the pH is lowered
further, releasing the Cu(II), and regenerating the
hydroxyoxime for recycle to the extraction stage.
Aqueous feeds (leach solution) typically contain more iron
per litre than copper. For commercial success, the extractant
must have a greater selectivity for Cu than Fe.
Hydrometallurgy of copper
3. Solution Purification: Solvent extraction
Extractants
Cu2+ forms square-planar complexes with hydroxyoxime:
R
1
N
O
R
Cu2+
1
N
O
R
R
O H
O H
Hydrometallurgy of copper
3. Solution Purification: Solvent extraction
Extractants
The
tris(salicylaldoximato)iron(III)
complex is octahedral, and no
extended planar ring structure
is possible between the 3
oxime ligands.
3+
Hydrometallurgy of copper
4. Metal Recovery:
At this point, the metal needs to be recovered from
solution in the solid form.
This is either achieved chemically, or
electrochemically.
Hydrometallurgy of copper
4. Metal Recovery:
Chemical recovery
Fe2+(aq) + Cu(s)
Reduction half-reactions:
Cu2+(aq) + 2e
Fe2+(aq) + 2e
Cu(s)
Fe(s)
E red = +0.34 V
E red = -0.44 V
Hydrometallurgy of copper
4. Metal Recovery:
Chemical recovery
Hydrometallurgy of copper
4. Metal Recovery:
Electrochemical recovery
Electrowinning
An electrochemical process for precipitating metals
from solution.
Hydrometallurgy of copper
4. Metal Recovery:
Electrochemical recovery
Electrowinning
A current is passed from an inert anode through a
liquid leach solution containing the metal so that the
metal is extracted as it is deposited onto the cathode.
The anode is made out of a material that will not
easily oxidise or dissolve, such as lead or titanium.
Hydrometallurgy of copper
4. Metal Recovery:
Electrochemical recovery
Electrorefining
The anodes consist of unrefined impure metal.
Current passes through the acidic electrolyte
corroding the anode into the solution.
Refined pure metal deposited onto the cathodes.
Metals with a greater E red than Cu (such as Zn and
Fe) remain in solution.
Metals with a lower E
as an anode sludge
refining.
red than
Hydrometallurgy of copper
4. Metal Recovery:
Electrorefining
Electrochemical recovery
Hydrometallurgy of copper
Summary:
Silicon production
/kJ mol-1
Ellingham diagrams
rG
Plot G vs T
(y = m X + c)
Temperature / C
Ellingham diagrams
Lower the position of a metal in the
Ellingham diagram = greater stability
of its oxide.
A metal found in the Ellingham
diagram can act as a reducing agent
for a metallic oxide found above it.
Stability of metallic oxides decrease
with increase in temperature.
Intersection of two lines imply the equilibrium of oxidation and
reduction reaction between two substances. Reduction possible
at the intersection point and higher temperatures where the G
line of the reductant is lower on diagram than the metallic
oxide.
Silicon production
rG
/kJ mol-1
Temperature / C
Silicon production
Silicon of between 96 to 99% purity is achieved by
reduction of quartzite or sand (SiO2, also called silica)
High temperatures required achieved in an electric arc
furnace.
Reduction carried out in the presence of excess silica
to prevent accumulation of silicon carbide (SiC) :
2SiO2(l) + 3C(s)
2SiC(s) + SiO2(l)
3Si(l) + 2CO(g)
Silicon production
The electric arc furnace
Silica and carbon fed in
through the top, liquid Si
collected at the bottom.
Temps of 2000K
achieved by an electric
arc burning between
graphite electrodes.
An arc forms between the charge and the electrodes.
The charge is heated both by current passing through the charge and
by the radiant energy evolved by the arc.
Silicon production
The electric arc furnace
Electric arc furnaces require huge amounts of electricity. A midsized furnace would have a transformer rated about 60,000,000
volt-amperes with a secondary voltage between 400 and 900
volts and a secondary current in excess of 44,000 amperes.
Silicon production
Applications
Si is the 2nd most abundant element in the earths
crust (~28%).
Principal constituent of natural stone, glass, concrete
& cement.
Silicon production
Applications
2nd largest application is in the
production of silicones. These are
polymers containing Si-O and Si-C
bonds. Typically heat-resistant,
nonstick, and rubberlike, they are
frequently used in cookware,
medical applications, sealants,
lubricants, and insulation.
Electronics industry ultra-pure silicon wafers used in
electronic components such as transistors, solar cells,
integrated circuits, microprocessors & various
semiconductor devices.
Silicon production
Purification
Ultra-pure silicon is required for the production of
semiconductors.
Silicon production
Purification
Semiconductor-grade Si produced by converting
crude Si to more volatile compounds like SiCl4.
These are then purified by exhaustive fractional
distillation.
Silicon production
Purification: The Czochralski process
Ultra-pure Si (only a few ppm of impurities) is melted in a crucible.
Dopant impurities (B or
P) can be added to
make n-type or p-type
silicon (influences the
electrical conductivity).
A seed crystal mounted
on a rod is dipped into
the molten Si.
Seed crystal rod pulled up & rotated at the same time.
By carefully controlling the temp gradients, rate of pulling, and
rotation speed, a large single-crystal (called a boule) can be
extracted from the melt.
Silicon production
Purification: The Czochralski process
Silicon production
Purification: The Czochralski process
The boule is then ground down
to a standard diameter and
sliced into wafers, much like a
salami.
Silicon production
Electrochemical preparation:
A new method that uses electrolysis to reduce SiO2 to
elemental Si.
Advantageous because it avoids the high energy costs
associated with the older carbothermic route, and also
reduces the CO2 emissions considerably.
SiO2 is usually an insulator, and doesnt conduct electricity,
but it has been shown that a tungsten wire sealed within a
quartz tube with the tungsten end exposed, can act as a
cathode.
Silicon production
Electrochemical preparation:
The anode is usually graphite, and the reduction is carried
out in a solution of molten CaCl2 at around 850 C.
a) SEM of W-SiO2 electrode
before reduction.
b) After reduction.
c) After washing.
d) Side view.
Silicon production
Electrochemical preparation:
Conversion of quartz to Si occurs at the three-phase
boundary between the SiO2, the electrolyte, and the flattened
end of the tungsten wire.
This provides enough impetus for the electrochemistry to
kick in properly as the silica is gradually converted to
conducting silicon.
This reaction should theoretically propagate through the
silica electrode, but in reality it grinds to a halt very quickly.
Reason for this is that the molten electrolyte cannot
penetrate through the newly formed Si layer on the surface.
three-phase boundary formation halted.
Silicon production
Electrochemical preparation:
Solution: replace solid quartz electrode with SiO2 powder
pressed into pellets & sintered.
Resulting electrode porous enough to allow electrolyte to
penetrate deeply into the material.
Silicon production
Electrochemical preparation:
Aluminium production
Most abundant metallic element in the earths crust.
But, extremely rare in its free form.
Once considered as a precious metal more valuable
than gold!
Al is a highly reactive metal that forms strong bonds
with O.
Requires a large amount of energy to extract from
Al2O3.
Aluminium production
Cannot be reduced directly by carbon since Al is a
stronger reducing agent than C.
Must therefore be extracted by electrolysis.
Aluminium production involves two steps: 1) purifying
Al2O3 from bauxite (the Bayer process) and 2)
converting Al2O3 to metallic Al (The Hall-Heroult
process).
Primary Al ore is bauxite, which consists of:
Gibbsite - Al(OH)3 (most extractable form)
Boehmite - AlOOH (less extractable than Gibbsite)
Diaspore - AlOOH (difficult to extract)
Aluminium production
The Bayer process: Step 1: Dissolution
The hydrated aluminium oxides are first selectively
dissolved from bauxite:
Al(OH)3 + NaOH
AlOOH + NaOH
2Na6Al6Si5O17(OH)10 + 10H2O
Aluminium production
The Bayer process: Step 2: Solid-Liquid Separation
The digested bauxite now consists of 1 liquid and 2
solid components:
Caustic liquid soln. with dissolved Al.
Undissolved coarse material (sand).
Precipitated fines (red mud).
Aluminium production
The Bayer process: Step 3: Precipitation
The remaining solution is supersaturated, containing
around 100-175 grams of dissolved Al(OH)3 per litre.
Al(OH)3 is precipitated out by adding seed crystals
since Al(OH)3 doesnt crystallise out easily on its own.
Once the crystals have reached the desired size, they
are removed, washed, and filtered.
The spent liquor is reheated, recausticised and
recycled.
Aluminium production
The Bayer process: Step 4: Calcination
Wet crystals of Al(OH)3, obtained from the
precipitation step are dried by heating to around 1300
1500 C.
This process also converts the Al(OH)3 to Al2O3:
2Al(OH)3 Al2O3 + 3H2O
Aluminium production
The Bayer process: Problems
Problems result from the coordination chemistry of Al
in basic solutions. Generally accepted structures:
Aluminium production
The Bayer process: Problems
In addition, the inertness of Al(III) leads to slow rates
of crystallisation, requiring large vessels & large
volumes of circulating solution & seed material.
Aluminium production
The Hall-Heroult process:
Reactive metals (e.g. Mg and Na) can be produced by
electrolysing a molten chloride salt of the metal.
Not the case for AlCl3 since it sublimes rather than
melts.
Even under sufficient pressure, molten AlCl3 is an
electrical insulator & cannot be used as an electrolyte.
Would have to be dissolved in a conductive salt (NaCl
or KCl).
Aluminium production
The Hall-Heroult process:
Cryolite is electrically conductive, and dissolves Al2O3.
Aluminium production
The Hall-Heroult process:
Anhydrous Al2O3 melts at over 2000 C which is too
high to be used as a molten medium for electrolytic
reduction of Al.
Al2O3 dissolved in cryolite has a m.p. of 1012 C & is a
good electrical conductor.
Graphite rods are used as anodes & are consumed in
the electrolytic process.
Aluminium production
The Hall-Heroult process:
The electrode reactions are as follows:
Anode: C(s) + 2O2-(l)
Cathode: 3e- + Al3+(l)
CO2(g) + 4eAl(l)
4Al(l) + 3CO2(g)
Aluminium production
The Hall-Heroult process:
Step 1: calculate the number of coulombs (C) from the
current (I) and the time (t):
Q=I t
= 10.0 A 3600 s
= 3.60 104 C
Step 2: find the number of moles of electrons:
Q
3.60 104 C
n
0.373 mol electrons
-1
F 96500 C mol
Aluminium production
The Hall-Heroult process:
Step 3: find the mass of Al produced:
3 mole of electrons needed to produce 1 mol of Al:
3e- + Al3+(l) Al(l)
Number of mol Al = 0.124
Mr Al = 26.98 g mol-1
mass Al = 26.98 g mol-1 0.124 mol
= 3.34 g Al
Aluminium production
The Hall-Heroult process:
Electrolytic reduction of Al is costly (3 e- required for
every atom of metallic Al reduced).
The electrical voltage used is only around 5.25 V, but
the current required is very high, typically 100,000 to
150,000 A or more!
Electrical power is the single largest cost in Al
production, Al smelters are typically located in areas
with inexpensive electric power, like S.A.
Pyrometallurgy of iron
Still the most important pyrometallurgical process
economically.
The most important sources of iron are hematite
(Fe2O3) and magnetite (Fe3O4).
Prehistorically, iron was prepared by simply heating it
with charcoal in a fired clay pot.
Today, the reduction of iron
oxides to the metal is
accomplished in a blast
furnace.
Pyrometallurgy of iron
Blast furnace:
1) Hot gas blast
2) Melting zone
3) Reduction of FeO
4) Reduction of Fe2O3
5) Pre-heating zone
6) Feed of ore,
limestone + coke
7) Exhaust gases
8) Column of ore, coke
+ limestone
9) Removal of slag
10) Tapping of molten pig iron
11) Waste gas collection
Pyrometallurgy of iron
The iron ore, limestone, and coke are added to the
top of the furnace.
Coke is coal that has been heated in an inert
atmosphere to drive off volatile components (~ 80
90% C).
Coke is the fuel, producing heat in the lower part of
the furnace. Is also the source of the reducing gases
CO & H2.
Limestone (CaCO3) serves as the source of CaO
which reacts with silicates & other impurities in the ore
to form slag.
Pyrometallurgy of iron
Slag:
Most rocks are composed of silica (SiO2) and silicates
(SiO32-) & are almost always present in the ore.
These compounds dont melt at the furnace
temperature & would eventually clog it up.
An important chemical method to remove these is by
use of a flux which combines with the silica & silicates
to produce a slag.
Slag collects at bottom of furnace & doesnt dissolve
in the molten metal.
Pyrometallurgy of iron
Slag:
The heat of the furnace decomposes the limestone to
give calcium oxide (e.g. of a calcination reaction).
CaO (a basic oxide) reacts with silicon dioxide to give
calcium silicate.
CaCO3(s)
CaO(s) + CO2(g)
CaO(s) + SiO2(s)
CaSiO3(l)
Pyrometallurgy of iron
Pyrometallurgy of iron
Air is blown into the bottom of the furnace, and
combusts with the coke to raise the furnace temp up
to 2000 C :
2C(s) + O2(g)
2CO(g)
H = -221 kJ
CO(g) + H2(g)
H = +131 kJ
Pyrometallurgy of iron
Molten iron is produced lower
down the furnace & removed.
Slag is less dense than iron &
can be drained away.
The iron formed (called pig iron)
still contains around 4-5% C, 0.61.2% Si, 0.4-2.0% Mn + S and P
and needs to be further
processed.
Pyrometallurgy of iron
At around 250 C (top of the furnace), limestone is
calcinated:
CaCO3(s)
CaO(s) + CO2(g)
Pyrometallurgy of iron
Cast iron
Cast iron is made by remelting pig iron & removing
impurities such as phosphorous and sulphur.
Pyrometallurgy of iron
Steelmaking
Pig iron is brittle, and not directly very useful as a
material.
Pyrometallurgy of iron
Steelmaking
Pyrometallurgy of iron
Types of iron & steel
Wrought iron iron with all the C removed. Soft &
easily worked with little structural strength. No longer
produced commercially.
Mild steel iron containing around 0.25% C. Stronger
& harder than pure iron. Has many uses including
nails, wire, car bodies, girders & bridges, etc.
High carbon steel contains around 1.5% C. Very
hard, but brittle. Used for things like cutting tools, and
masonry nails.
Pyrometallurgy of iron
Types of iron & steel
Stainless steel iron mixed with chromium and nickel.
Resistant to corrosion. Uses include cutlery, cooking
utensils, kitchen sinks, etc.
Titanium steel iron mixed with titanium. Withstands
high temperatures. Uses include gas turbines,
spacecraft parts, etc.
Manganese steel iron mixed with manganese. Very
hard. Uses include rock-breaking machinery, military
helmets, etc.
Pyrometallurgy of iron
The thermite reaction
Aluminium metal can reduce Iron(III) oxide (Fe2O3) in
a highly exothermic reaction.
Molten iron is produced at around 3000 C.
Reaction used for thermite welding, often used to join
railway tracks.
Fe2O3(s) + 2Al(s)
2Fe(s) + Al2O3(s)
Pyrometallurgy of iron
The thermite reaction
Pyrometallurgy of iron
The thermite reaction
Fe2O3(s) + 2Al(s)
2Fe(l) + Al2O3(s)
Hfo (kJ/mol)
Fe2O3(s)
-822.2
Al(s)
Al2O3(s)
-1,669.8
Fe(s)
Exothermic!
Electrowinning of iron
The Pyror process:
Studies into iron extraction by electrowinning from
sulphate solutions were first carried out around 50
years ago, then subsequently forgotten.
May become important again in the future as new,
more environmentally friendly methods are sought for
steelmaking.
Electrowinning of iron
The Pyror process:
FeSO4(l) + H2S(g)
Electrowinning of iron
The Pyror process:
Step 4: Electrolysis. Iron is reduced and deposited
on the cathode, while O2 is evolved, and H2SO4 is
regenerated at the anode. More specifically:
At the cathode:
Fe2+ + 2eFe(s)
2H+ + 2eH2(g)
Fe3+ + eFe2+
At the anode:
SO42- + H2O
Fe2+
Fe3+ + e-
Electrowinning of iron
The Pyror process:
Electrowinning of iron
The Pyror process:
Electrowinning of iron
The Pyror process:
Gold extraction
Gold mining
Historical:
Gold extraction
Gold mining
Historical:
Gold extraction
Gold mining
Modern methods:
Gold extraction
Gold ore processing
Gold cyanidation:
4NaAu(CN)2(l) + 4NaOH(l)
Gold extraction
Gold ore processing
Gold cyanidation:
Agitated leaching
Gold extraction
Gold ore processing
Gold cyanidation:
Gold extraction
Gold ore processing
Gold cyanidation:
Heap leaching
Gold extraction
Gold ore processing
Gold cyanidation:
Heap leaching
Gold extraction
Gold ore processing
Gold cyanidation:
Heap leaching
Gold extraction
Gold ore processing
Gold recovery:
Gold extraction
Gold ore processing
Gold recovery:
Gold extraction
Gold ore processing
Gold recovery:
Gold extraction
Gold ore processing
Gold recovery:
1) Carbon in pulp
Gold extraction
Gold ore processing
Gold recovery:
1) Carbon in pulp
Gold extraction
Carbon in pulp
Gold extraction
Gold ore processing
Gold recovery:
2) Merrill-Crowe process
Gold extraction
Gold ore processing
Gold recovery:
2) Merrill-Crowe process