CuS(s) + 2O2(g) → CuSO4(aq) + SO2(g

Extraction Metallurgy
Part 2: Case studies
Dr. C.B. Perry (C306)
http://www.gh.wits.ac.za/chemnotes
Chem 3033
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.
Aluminium Electrolytic reduction.
The siderophiles The extraction of Au and the Pt group metals

and their purification.
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.
2. Roasting: a metallurgical treatment involving gas-

solids reactions at elevated temperatures.
3. Smelting: a melting process which separates the

chemical reaction products into 2 or more layers.
4. Refining: treatment of a crude metal product to improve its

purity.
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).
The following steps are involved in Cu extraction:
1. Concentration
2. Roasting
3. Smelting
4. Conversion
5. Refining
1. Concentration
Finely crushed ore concentrated by the froth-flotation
process:
Ground ore mixed with xanthates (salts & esters of
xanthic acid), dithiophosphates, or thionocarbamates.
These make the ore surface hydrophobic.
Ore then introduced into a water bath where 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.
1. Concentration (cont.)
The froth containing the Cu ore is skimmed off and
reprocessed.
The remaining material (sand particles & other

impurities) sink to the bottom & is discarded or
reprocessed to extract other elements.
1. Concentration (cont.)
Froth-flotation
2. Roasting
Involves partial oxidation of the sulphide mineral with
air at between 500C and 700C.
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.
The gases produced contain around 5 15% SO2, which
is used for sulphuric acid production.
2. Roasting (cont.)
Objectives of roasting:
1) Remove part of the sulphur.
2) Convert iron sulphides into iron oxide and iron

sulphate to facilitate removal during smelting.
3) To pre-heat the concentrate to reduce amount of

energy needed by the smelter.
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 1200C, 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.
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:
FeS(l) + 6CuO(l) 3Cu2O(l) + FeO(l) + SO2(g)

FeS(l) + Cu2O(l) FeO(l) + Cu2S(l)
Cu2S(l) + FeS(l) Cu2SFeS(l) (matte)
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.
4. Conversion (cont.)
Iron removal
A silica flux is added to keep the slag (see below)
molten.
Air is blown into the converter to oxidize the iron
sulphide according to the following reaction:
2Cu2SFeS(l) + 3O2(g) + SiO2(l) 2FeOSiO2(l) + 2SO2(g) + Cu2S(l)
The oxidized Fe and Si form a slag (insoluble in

matte) that is skimmed off & disposed off.
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.
5. Refining
The 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.
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) 2e-
Cu2+(aq) + 2e- Cu(s) Ered = -0.83V
5. Refining (cont.)
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.
Hidrometalurgia del Cu
Ventajas
Ms amigable con el medio ambiente que la
Pirometalurgia.
Comparado con la Pirometalurgia, solo una fraccin
de los gases se libera al medio.
Emisin de partculas slidas prcticamente
inexistente.
Desventajas
Se utilizan grandes cantidades de agua, mayor
potencial de contaminacin.
Aguas de desecho contienen compuestos metlicos
solubles, compuestos quelantes y solvents orgnicos.
Involucra los siguientes pasos
1. Preparacin de la Mena
2. Lixiviacin
3. Purificacin de la Solucin
4. Recuperacin del Metal

Hydrometallurgy of copper
1. Preparacin de la mena
Se somete la mena a un grado de conminucin para
liberar los xidos de Cu y sulfuros a la solucin
lixiviante.
1. Preparacin de la Mena
Grado de conminucin depende de la calidad de la
mena:
Menas de alta ley Mayor conminucin
Menas de baja ley Menor conminucin
(Why??)
De ser possible se pre concentra la mena; separacin
de mena de baja ley de Cu.
2. Lixiviacin
Definicin: La disolucin de un mineral en un solvent,
dejando la ganga como un slido no disuelto.
Cu normalmente de lixivia mediante tres procesos:

(a) Lixiviacin en Botaderos
(b) Lixiviacin en Pilas
(c) Lixiviacin Bacteriana

2. Lixiviacin (a) Lixiviacin en
Botaderos
La solucin lixiviante se roca sobre el botadero.

La solucin que escurre se recolecta y se recupera el Cu de
esta.
Proceso lento que toma meses o aos en completar.
Tpicamente se recupera apenas el 60% de Cu del botadero.
2. Lixiviacin (b) Lixiviacin en
Pilas
Similar a la lixiviacin en botaderos except que el material

no se arroja simplemente, se lo lleva a un tamao de grava y
se apila en un pad artificial.
Luego de la lixiviacin (6 meses a 1 ao) se remueve la
ganga del pad, se deshace de sta y se reemplaza con
mena fresca.
2. Lixiviacin
Reacciones de Lixiviacin
La naturaleza de la mena determina si la lixiviacin es oxidante
o no oxidante.
Lixiviacin no oxidante: No hay cambio en el estado de
oxidacin.
e.g. (1) Disolucin del sulfato de Cu por agua:
CuSO4(s) + H2O(l) Cu2+(aq) + SO42-(aq)
(2) Disolucin de materiales alcalinos por cidos

Cu2(OH)2CO3(s) + 2H2SO4(aq) 2CuSO4(aq) + CO2(g) + 3H2O(l)
2. Lixiviacin
Lixiviacin Oxidante: Muchas menas son nicamente
solubles cuando han sido oxidadas
e.g. Covelina (CuS) mucho ms soluble si se oxide a CuSO4
CuS(s) + O2(g) CuSO4(aq)
EJERCICIO: Identificar que especie es oxidada, y cual
reducida, escribir el balance de la reaccin parcial para cada
una.
SOLUTION: CuS Cu = +2, S = -2
O2 O=0
CuSO4 Cu = +2, O4 = -8, S = +6
S-2 S+6 + 8e- (oxidation)

2O2 + 8e- 4O2- (reduction)
2. Lixiviacin (c) Bacteriana
Muchas bacterias, especialmente Thiobacilus, son
capaces de solubilizar metals oxidando el hierro
ferroso a hierro frrico, as como tambin azufre
elemental, sulfuros, sulfatos y otros compuestos
sulfurosos a cido sulfrico o sulfatos.
20 al 25% de Cu producido en USA, y 5% del Cu

mundial es obtenido por lixiviacin bacteriana.
Proceso muy lento, puede tomar aos para Buena

recuperacin.
Bajos costos de operacin y de inversion.
2. Lixiviacin (c) Lixiviacin
Thiobacilli Bacteriana
Son cido tolerantes, algunas crecen a un pH tan bajo

como 0.5.
Son tolerantes ante toxicidades altas.
Son quimiolitoauttrofos (La fuente de C es CO2 & la

energa es derivada de la transformacin qumica de
material inorgnica).
Mecanismo Bacteriana
Reaccin Generalisada: M(II)S + 2O2 M2+ + SO42-
Dos mecanismos: (a) mecanismo indirecto

involucrando el ciclo frrico ferroso, y (b)
mecanismo directo involucrando el contacto fsico del
organism con el sulfuro mineral.
Mecanismo: Indirecta Bacteriana
Primer paso: sulfato ferroso se convierte en sulfato

frrico por la accin del Acidithiobaccilus Ferrooxidans:
4FeSO4 + O2 + 2H2SO4 2Fe2(SO4)3 + 2H2O
EJERCICIO: identifica cual es sulfato frrico y sulfato ferroso,

escriba las reacciones parciales para cada una.
FeSO4 SO42- Fe2+ (ferrous)

2Fe2(SO4)3 3 SO42- = -6, but 2 Fe Fe3+ (ferric)
Mecanismo: Indirecto Bacteriana
2Fe2+ 2Fe3+ + 2e- (oxidation)

O2 + 2e- 2O2- (reduction)
El sulfato frrico es un agente oxidante fuerte capaz

de dissolver un rango de minerals sulfurosos.
En el caso de la calcopirita:
CuFeS2 + 2Fe2(SO4)3 CuSO4 + 5FeSO4 + 2S
El S elemental producido de manera indirecta puede

ser convertido en H2SO4 por el Acidithiobacillus
ferrooxidans:
El H2SO4 ayuda a mantener el pH a niveles

favorables para la actividad bacteriana.
La bacteria se adhiere a la superficie mineral previo al

ataque enzimtico.
El mineral se oxida con sulfato y cationes metlicos
En el caso de la covelina:
CuS + 2O2 CuSO4

3. Purificacin de la solucin
Las reacciones de lixiviacin no son perfectamente
selectivas: se tienen otros elementos en solucin, no
solamente Cu. Estos deben ser removidos.
Despues de la lixiviacin el Cu en solucin puede

estar muy diluido: se necesita de una forma de
concentrarlo.
Ambos procesos se hacen usualmente mediante

procesos de intercambio inico, los dos ms
communes siendo cromatografa de intercambio
inico, y extraccin por solvente.
Cromatografa de Intercambio Inico
DEFINICIN: Una solucin conteniendo una mexcla
de iones metlicos es puesta en contacto con una
resina que es insoluble en la solucin metal-ion.
La resina consiste de un fase slida inerte hacia la
cual los grupos funcionales son unidos qumicamente.
Los grupos funcionales pueden ser cidicos (H+) o

bsicos (OH) grupos que se intercambian con
cationes (M+) o aniones (M), respectivamente.
El proceso de intercambio inico es reversible.
Ion exchange chromatography
Grupos carboxilos intercambian el ion (H+) por un ion

Cu2+
El Cu2+ se libera luego ponindolo en contacto con
una solucin removedora (alta conc. de H+).
3. Purificacin de la Extraccin por
solucin: Solvente
DEFINICIN: un mtodo para separar compuestos

basados en sus solubilidades relativas en 2 lquidos
diferentes inmiscibles.
En la industria, esto se lo instala como un proceso

continuo.
3. Purificacin de la Extraccin por
Solucin: Solvente
Extraccin por
3. Purificacin de la Solucin: Solvente
Corriente orgnica acuosa + bombeada en un mezclador.
Mezcla con componentes orgnicos (conteniendo un
extractante) y acuosos, ocurre una transferencia de iones
entre ellos.
Una vez que la transferencia de iones se complete
(equilibrio) la mezcla se separa.
La solucin acuosa se remueve y la fase orgnica
(conteniendo Cu2+) se mezcla con una solucin extractor
acuosa.
El Cu2+ regresa a fase acuosa, y las dos fases se separan
de Nuevo.
La fase acuosa (conteniendo el Cu2+) se remueve y la
fase orgnica es reciclada hacia el mezclador.
3. Purificacin de la Solucin: Extraccin por
solventes
Extractantes
Los mejores extractantes para el Cu son los de tipo ortho-
hydroxyoxime:
OH
OH N
R = alkyl ,phenyl, or H
R R1 = alkyl
1
R
Funcin por medio de un mecanismo de intercambio
catinico dependiente del pH:
Cu2+ + 2HA CuA2 + 2H+
(dondeH en HA denota un proton reemplazable)
3. Purificacin de la solucin: Extraccin por
solvente
Extractantes
A pH bajos (1.5 2.0) el ortho-hydroxyoxime transforma el
Cu en un in complejo.
Durante la extraccin el pH baja ms, liberando el Cu y

regenerando el hydroxyoxime para recilarlo a la etapa de
extraccin.
La alimentacin acuosa (solucin lixiviante) contiene

tpicamente ms hierro por litro que Cu. Para uso
commercial, el extractante debe tener una major selectividad
para el Cu que de Fe.
solventes
Extractantes
El Cu2+ forma complejos cuadrados-planares con
O H
hydroxyoxime: R
1
R O N
Cu
1
N O R
R O H
Unin de H entre el H oxmico y el O fenlico soportan la
estabilidad 2:1 de este complejo.
La constant de formacin (K2) para el complejo 2:1 es

mucho mayor que para el complejo 1:1.
Extractantes solventes
El compuesto tris(salicylaldoximato)iron(III) es octahedral, y
no es possible una estructura anular planar extendida entre
los 3 ximas ligando.
la estabilidad del complejo Fe(III) es menor que la del

complejo Cu(II), que permite que la extraccin del Cu sea
llevada a cabo a un pH menor que el que es requerido para
una eficiente extraccin de Fe.
4. Recuperacin del
Metal:
En este punto, el metal necesita ser recuperado de la
solucin en forma slida.
Esto se realiza de manera qumica o electroqumica.

4. Recuperacin del Metal: Recuperacin
Qumica
El Cu disuelto se depositar en en una superficie de
Fe de acuerdo a la siguiente reaccin:
Cu2+(aq) + Fe(s) Fe2+(aq) + Cu(s)
Why??
Reduccin de las reacciones parciales:
Cu2+(aq) + 2e Cu(s) Ered = +0.34 V
Fe2+(aq) + 2e Fe(s) Ered = -0.44 V
Ered para la reaccin parcial del Cu2+ es ms positive
que para la reaccin parcial de Fe2+, lo que conduce a
que el Cu se reduzca y el Fe se oxide.
Recuperacin
4. Recuperacin del Metal: Qumica
Soluciones que contienen Cu se hacen apsar a travs

de una capa de chatarra triturada, resultando en que
los iones de Cu se depositen como Cu slido en la
superficie de Fe.
Para que el proceso sea eficiente, la superficie de

chatarra metlica debse ser amplia.
4. Recuperacin del metal: Recuperacin
Electroqumica
Electrowinning
Un proceso electroqumico para precipitar metales en
solucin.
4. Recuperacin del metal: Recuperacin
electroqumica
Electrowinning
Se pasa corriente de un nodo inerte a travs de la

solucin lixiviante que contiene el metal, de tal
manera que el metal es extrado a medida que que
deposita en el ctodo.
El nodo est hecho de un material que no se oxide

fcilmente ni se disuelve, como plomo o titanio.
4. Metal Recovery: Recuperacin
Electrorefinamiento electroqumica
Los nodos consisten de metal impuro sin refinar.

Se pasa corriente a travs del electrolito cido
corroyendo el nodo en la solucin.
El metal puro refinado se deposita en los ctodos.
Metales con mayor Ered que el Cu (como Zn y Fe)
permanecen en solucin.
Metales con menor Ered que el Cu (Au, Ag) se
acumulan como lodo de nodo recolectados y
vendidos para refinacin posterior.
Recuperacin
4. Recuperacin del metal:
electroqumica
Electrorefining
Summary:
Silicon production
More difficult to extract Si than either Cu or Fe.
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) :
SiO2(l) + 2C(s) Si(l) + 2CO2(g)

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 mid-

sized 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.
Largest application of pure Si (metallurgical grade) is
in the manufacture of Al-Si alloys to produce cast
parts (for automotive industry).
Important constituent of electrical steel (modifies the
resistivity & ferromagnetic properties).
Added to molten cast iron to improve its performance
in casting thin sections.
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.
Reduced back to Si with pure H2.
Finally, the high-purity Si is melted and large single
crystals are grown by the Czochralski process.
Electronic grade Si is required to be 99.999999999%
pure!
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
Silicon production
The boule is then ground down
to a standard diameter and
sliced into wafers, much like a
salami.
The wafers are etched and

polished, and move on to the
process line.
A point to note however, is that due to "kerf" losses (the width

of the saw blade) as well as polishing losses, more than half
of the carefully grown, very pure, single crystal silicon is
thrown away before the circuit fabrication process even
begins!
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
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
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
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.
a) SEM of SiO2 powder

b) reduced Si powder.
Silicon production
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.
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)
The Bayer process: Step 1: Dissolution
The hydrated aluminium oxides are first selectively
dissolved from bauxite:
Al(OH)3 + NaOH NaAlO2 + 2H2O (Gibbsite dissolution)
AlOOH + NaOH NaAlO2 + H2O (Boehmite dissolution)
An undesirable side reaction is the formation of red

mud, which occurs when Al(OH)3 reacts with
dissolved Kaolinite clay:
5Al2Si2O5(OH)4 + 2Al(OH)3 + 12NaOH 2Na6Al6Si5O17(OH)10 + 10H2O
Red mud formation consumes dissolved Al and

represents a Al loss.
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).
Sand (mainly undissolved silicates) easily removed
since they settle very rapidly.
The red mud is removed by adding a flocculent to
increase the settling rate.
The Al content of the red mud is recovered & forms
part of the liquid layer.
The Bayer process: Step 3: Precipitation
The remaining solution is supersaturated, containing
around 100-175 grams of dissolved Al2O3 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.
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
The Bayer process: Problems
Problems result from the coordination chemistry of Al
in basic solutions. Generally accepted structures:
Leads to extensive H-bonding between aluminate ion

& solvent, which in turn leads to high viscosity of these
solutions.
In turn leads to problems with materials handling &
heat exchange.
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.
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).
Commercially viable production of Al only commenced
once the use of cryolite (Na3AlF6) was discovered.
Cryolite is electrically conductive, and dissolves Al2O3.
Anhydrous Al2O3 melts at over 2000C 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 1012C & is a

good electrical conductor.
Graphite rods are used as anodes & are consumed in

the electrolytic process.
The cathode is a steel vessel, lined with graphite.

The electrode reactions are as follows:
Anode: C(s) + 2O2-(l) CO2(g) + 4e-
Cathode: 3e- + Al3+(l) Al(l)
CLASS EXERCISE : Write out the balanced overall reaction
4Al3+(l) + 6O2-(l) + 3C(s) 4Al(l) + 3CO2(g)
CLASS EXERCISE : Calculate the mass of Al that will be

produced in 1.00 hr by the electrolysis of molten AlCl3, using a
current of 10.0 A.
Step 1: calculate the number of coulombs (C) from the
current (I) and the time (t):
Q=It
= 10.0 A 3600 s
= 3.60 104 C
Step 2: find the number of moles of electrons:
Q 3.60 104 C
n -1
0.373 mol electrons
F 96500 C mol
F (Faraday constant) = magnitude of electric charge per mole

of electrons.
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
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.
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
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.
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.
Slag:
The heat of the furnace decomposes the limestone to
give calcium oxide.
CaO (a basic oxide) reacts with silicon dioxide to give

calcium silicate.
CaCO3(s) CaO(s) + CO2(g)
CaO(s) + SiO2(s) CaSiO3(l)
Slag helps protect the molten iron from re-oxidation.
Slag is used in road making, and can also be

combined with cement.
Air is blown into the bottom of the furnace, and
combusts with the coke to raise the furnace temp up
to 2000C :
2C(s) + O2(g) 2CO(g) H = -221 kJ
H2O in the air also reacts with the coke:

C(s) + H2O(g) CO(g) + H2(g) H = +131 kJ
Since this reaction is endothermic, if the blast furnace

gets too hot, water vapor is added to cool it down
without interrupting the chemistry.
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, 0.6-
1.2% Si, 0.4-2.0% Mn + S and P
and needs to be further
processed.
At around 250C (top of the furnace), limestone is
calcinated:
CaCO3(s) CaO(s) + CO2(g)
Also at the top of the furnace, hematite is reduced:

3Fe2O3(s) + CO(g) 2Fe3O4(s) + CO2(g)
Reduction of Fe3O4 occurs further down the furnace

(~700C):
Fe3O4(s) + CO(g) 3FeO(s) + CO2(g)
Near the middle of the furnace (1000C) Fe is
produced:
FeO(s) + CO(g) Fe(s) + CO2(g)
Cast iron
Cast iron is made by remelting pig iron & removing
impurities such as phosphorous and sulphur.
The viscosity of cast iron is very low, & it doesnt
shrink much when it solidifies.
ideal for making castings.
BUT, it is very impure, containing up to 4% carbon.
This makes it very hard, but also very brittle.
Shatters rather than deforms when struck hard.
These days cast iron is quite rare, often being
replaced by other materials.
Steelmaking
Pig iron is brittle, and not directly very useful as a
material.
Typically, pig iron is drained directly from the blast
furnace (referred to as hot metal), and transported to
a steelmaking plant while still hot.
The impurities are removed by oxidation in a vessel
called a converter.
The oxidising agent is pure O2 or O2 mixed with Ar.
Air cant be used as N2 reacts with iron to form iron
nitride which is brittle.
Steelmaking
O2 blown directly into molten
metal.
Reacts exothermically with
C, Si + other impurities.
C & S expelled as CO and
SO2 gas.
Si oxidised to SiO2 &
incorporates into the slag
layer.
Once oxidation complete,
Iron converter contents poured out &
various alloying elements
added to produce steels.
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.
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.
The thermite reaction
Aluminium metal can reduce Iron(III) oxide (Fe2O3) in

a highly exothermic reaction.
Molten iron is produced at around 3000C.
Reaction used for thermite welding, often used to join

railway tracks.
Fe2O3(s) + 2Al(s) 2Fe(s) + Al2O3(s)

Fe2O3(s) + 2Al(s) 2Fe(l) + Al2O3(s)
CLASS EXERCISE : calculate the thermal energy that is
released in the reaction.
Component Hfo (kJ/mol)
Fe2O3(s) -822.2
Al(s) 0
Al2O3(s) -1,669.8
Fe(s) 0
Horxn = (1 mol)(HfoAl2O3) + (2 mol)(HfoFe) - (1 mol)(HfoFe2O3) - (2 mol)(HfoAl)
Horxn = (1 mol)(-1,669.8 kJ/mol) + (2 mol)(0) - (1 mol)(-822.2 kJ/mol) - (2mol)(0 kJ/mol)
Horxn = -847.6 kJ mol-1 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.
The Pyror process:
First step is to convert iron pyrite (FeS2) into an acid
soluble form (FeS). Achieved by either calcining at
800 to 900 C to expel a loosely-bound S, or by
smelting in an electric furnace.
Step 2 is a leaching step using H2SO4 to extract iron

from FeS:
FeS(s) + H2SO4(l) FeSO4(l) + H2S(g)
Step 3: before entering the electrowinning cells, the
solution is purged with air to remove any remaining
H2S.
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+ + 2e- Fe(s)
2H+ + 2e- H2(g)
Fe3+ + e- Fe2+
At the anode:
SO42- + H2O H2SO4 + 1/2O2 + 2e-
Fe2+ Fe3+ + e-
The Pyror process:
The Pyror process:
The process was shown to
be quite efficient. During a 2
year pilot-plant project, a
quantity of iron close to 150
tonnes was produced.
Electrolysis was run for several weeks before

stripping was performed, resulting in deposits of
13mm or more in thickness.
The Pyror process:
Gold extraction
Gold mining Historical:
Panning sand and gravel
containing gold is shaken around
with water in a pan. Gold is much
denser than rock, so quickly
settles to the bottom of the pan.
Gold extraction
Gold mining Historical:
Sluicing water is channelled to
flow through a sluice-box. Sluce-
box is essentially a man-made
channel with riffles (barriers) at the
bottom. Riffles create dead-zones
in the water current which allows
gold to drop out of suspension.
Sluicing and panning results in the direct recovery of

small gold nuggets and flakes.
Gold extraction
Gold mining Modern methods:
Hard rock mining used
to extract gold encased in
rock. Either open pit
mining or underground
mining.
Gold extraction
Gold ore processing Gold cyanidation:
The most commonly used process for gold extraction.
Used to extract gold from low-grade ore.
Gold is oxidised to a water-soluble aurocyanide

metallic complex.
In this dissolution process, the milled ore is agitated

with dilute alkaline cyanide solution, and air is
introduced:
4Au(s) + 8NaCN(l) + O2(g) + 2H2O(l) 4NaAu(CN)2(l) + 4NaOH(l)
Gold extraction
At a slurry concentration of around 50% solids, the

slurry passes through a series of agitated mixing tanks
with a residence time of 24 hrs.
The gold-bearing liquid is then separated from the

leached solids in thickener tanks or vacuum filters &
the tailings are washed to remove Au and CN- prior to
disposal.
Gold extraction
The aurocyanide complex has an exceptionally high

stability constant, 2 [Au(CN)2]- = 2 1038.
This high stability constant means that dissolution can

be achieved even in the presence of considerable
amounts of other metals (Cu, Zn, and Ni).
At this point, the dissolved Au needs to be recovered

from the cyanide solution. Two methods commonly
used to achieve this are 1) the Carbon in pulp
process, and 2) the Merrill-Crowe process.
Gold extraction
Gold ore processing Heap Leaching
Is an alternative to the agitated leaching process.

Drastically reduced gold recovery costs of low grade
ore.
Ore grades as low as 0.3 g per ton can be
economically processed by heap leaching.
Gold extraction
Gold ore processing Heap Leaching
Generally requires 60 to 90 days for processing ore

that could be leached in 24 hrs in a conventional
agitated leach process.
Au recovery is around 70% as compared with 90% in
an agitated leach plant.
BUT, has gained wide favour due to vastly reduced
processing costs.
Frequently, mines will use agitated leaching for high-
grade ore & heap leaching for marginal grade ores
that would otherwise be considered waste rock.
Gold extraction
1) Carbon in pulp overview:
Dissolved aurocyanide is mixed with free activated
carbon particles in solution and agitated in leach tanks.
The carbon particles are much larger than the ground
ore particles.
Gold has a natural affinity for C, and the aurocyanide
complex is adsorbed onto the C.
The coarse C particles with bound [Au(CN)2]- are then
removed by screening using a wire mesh. Finely ground
ore passes through the mesh.
Gold extraction
1) Carbon in pulp details:
On completion of cyanidation, pregnant pulp is

transferred to Carbon In Pulp (CIP) process.
Pregnant pulp passed through a number of tanks (5 or
6) in series. Tanks are mechanically stirred.
Granulated carbon is pumped counter-current to the
pulp through the tanks.
In the final tank, fresh, or barren carbon comes into
contact with low-grade or tailings solution.
Gold extraction
1) Carbon in pulp details:
In this tank, the barren carbon has a high activity, and

can remove trace amounts of Au < 0.01 mg / L.
As the carbon passes through the tanks, it collects

increasing quantities of Au from the solution. This is
termed loading.
Typically, concentrations as high as 4000 to 8000 g Au /

ton of C can be achieved on the final loaded C.
Gold extraction
1) Carbon in pulp
The loaded carbon is separated from the pulp in the final

tank & transferred to the elution circuit.
Barren pulp is dewatered (to recycle water & remove
cyanide for reuse in the process).
In the elution circuit, the loaded carbon is treated with a
hot cyanide & caustic solution to remove the Au.
The barren carbon is reactivated & recycled for use in
the process.
Gold extraction
1) Carbon in pulp
The cyanide & caustic solution is transferred to an
electrowinning circuit where the Au is plated out onto
steel wool.
The Au-plated steel wool is transferred to the smelting

circuit to produce gold bullion.
Gold extraction
Carbon in pulp
Gold extraction
2) Merrill-Crowe process
Traditional method for Au recovery from pregnant

cyanide solutions.
Once dissolution of Au is complete, the remaining rock

pulp if filtered off through various filters &
diatomaceous earth to produce a sparkling clear
solution.
O2 is removed from the clarified solution by passing

the solution through a vacuum deaeration column.
Gold extraction
2) Merrill-Crowe process
Zinc dust is then added to the cyanide solution to

chemically reduce the gold to the metal.
The metallic gold is then filtered out & refined.

CuS(s) + 2O2(g) → CuSO4(aq) + SO2(g

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CuS(s) + 2O2(g) → CuSO4(aq) + SO2(g

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Extraction Metallurgy

Part 2: Case studies

Dr. C.B. Perry (C306)

Hydrometallurgical processes ion exchange processes,

Iron Pyrometallurgy and the blast furnace.

Silicon The electric arc furnace. Purification by the Czochralski

Aluminium Electrolytic reduction.

The siderophiles The extraction of Au and the Pt group metals

2. Roasting: a metallurgical treatment involving gas-

3. Smelting: a melting process which separates the

4. Refining: treatment of a crude metal product to improve its

Most common source of Cu ore is the mineral

Other important ores include:

Ore then introduced into a water bath where air is

Finely divided hydrophobic ore particles latch on to the

The remaining material (sand particles & other

1) Remove part of the sulphur.

2) Convert iron sulphides into iron oxide and iron

3) To pre-heat the concentrate to reduce amount of

Smelting is carried out at around 1200C, usually with a

FeS(l) + 6CuO(l) 3Cu2O(l) + FeO(l) + SO2(g)

The sulphur is removed by selective oxidation of the

Converting is carried out in two stages: 1) an iron

The oxidized Fe and Si form a slag (insoluble in

The end product is around 98.5% pure & is known as

The anodes (cast from blister copper) are placed into

Thin sheets of highly pure Cu serve as the cathodes.

Application of a suitable voltage causes oxidation of

Cu2+ ions migrate through the electrolyte to the

Metallic impurities more active then Cu are oxidized at

Large amount of gases produced present air pollution

Dust produced contains heavy metals such as

Waste water contaminated with:

4. Recuperacin del Metal

Cu normalmente de lixivia mediante tres procesos:

(b) Lixiviacin en Pilas

(c) Lixiviacin Bacteriana

La solucin lixiviante se roca sobre el botadero.

Similar a la lixiviacin en botaderos except que el material

(2) Disolucin de materiales alcalinos por cidos

S-2 S+6 + 8e- (oxidation)

20 al 25% de Cu producido en USA, y 5% del Cu

Proceso muy lento, puede tomar aos para Buena

Son cido tolerantes, algunas crecen a un pH tan bajo

Son tolerantes ante toxicidades altas.

Son quimiolitoauttrofos (La fuente de C es CO2 & la

Reaccin Generalisada: M(II)S + 2O2 M2+ + SO42-

Dos mecanismos: (a) mecanismo indirecto

Primer paso: sulfato ferroso se convierte en sulfato

EJERCICIO: identifica cual es sulfato frrico y sulfato ferroso,

FeSO4 SO42- Fe2+ (ferrous)

2Fe2+ 2Fe3+ + 2e- (oxidation)

El sulfato frrico es un agente oxidante fuerte capaz

El S elemental producido de manera indirecta puede

El H2SO4 ayuda a mantener el pH a niveles

La bacteria se adhiere a la superficie mineral previo al

El mineral se oxida con sulfato y cationes metlicos

CuS + 2O2 CuSO4

Despues de la lixiviacin el Cu en solucin puede

Ambos procesos se hacen usualmente mediante

Los grupos funcionales pueden ser cidicos (H+) o

Grupos carboxilos intercambian el ion (H+) por un ion