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Extraction of Aluminium

Appearance: silvery gray metallic

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General properties

• Atomic number (Z) 13

• Atomic weight 26.98
• Melting Point 933.47 K ​(660.32 °C, ​1220.58 °F)
• Boiling Point 2743 K ​(2470 °C, ​4478 °F)
• Density RT 2.70 g/cm3
• when liquid, at m.p.2.375 g/cm3
• Crystal Structure FCC
• Oxidation state +3

Aluminium – Properties
• Ductility and flow properties
• High corrosion resistance and non-toxic properties
• Rolling properties and ability to acquire brilliant surface finish
• High reflectivity and low emissivity
• Excellent electrical conductivity
• High strength to weight ratio
• High thermal/electrical conductivity

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Aluminium – Applications
• In impact extrusion of vessels and containers of various shapes
• In kitchenware, chemical, and brewing industries, and milk processing
• In packing industry and decorative protective surface
• In roofing systems and thermal insultion either as metal foil or aluminium
paint
• In aluminium alloys in transport industries and structural application
• In electrical conductors
• Deoxidizing

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The raw materials used in aluminium purification

Ores
• primarily a mixture of Gibbisite & Diaspore
– Al2O3.3H2O Gibbisite (65.4 %)
– Al2O3. H2O Diaspore (85.4 %)
– Fe2O3 , TiO2 and SiO2
– Al2O3 Indian ores 58 - 67 %
• High TiO2 5-10%, SiO2 0.5 -2.0%
• Ores of Kashmir are mainly Diaspore(75% Al2O3 )
• No TiO2 high Silica around 5%
• High Silica renders difficult for Bayers process
• Red mud is insoluble residue during leaching Na2O Al2O3 3 SiO

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Al Extraction
• Carbothermic reduction is not commercially viable
– High temperature 2000o C
– At this temperature undesirable alumina carbide forms
– Refractories to maintain such high temperature are not only expensive
but also not readily available.

• Electrolysis of aqueous solution from salts is not feasible

– Deposition of aqueous solution leads to evolution of H occurs at much
lower potential than potential required for Al production.
– Hydrogen over potential is insufficient to overcome the 1.67 V difference
between Al Deposition and H evolution.

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The solution for the difficulties in Al extraction is ---- Hall Heroult Process

Electrolysis process using fused electrolyte.

Electrolyte is prepared by : Dissolving Al2O3 in Cryolite (3NaF.AlF3)

From Bauxite, Alumina is produced by Bayer process.

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Bayer Process

▪ Austrian chemist Karl Josef Bayer

▪ The pressure leaching of bauxite with NaOH
solution to obtain sodium aluminate solution.
▪ 220oC , 5-25 atm pressure
▪ The precipitation of pure aluminum hydroxide
from this solution by seeding with fine crystals
of Al(OH)3.

Aerial view of a Bayer processing plant

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Main aim of Bayer process is to extract high purity Alumina from bauxite.

In this process, digesting crushed bauxite in strong sodium hydroxide (NaOH) solution
at Temp 180-2200C, 5-25atm, 2.5hrs to form Sodium Aluminate from which Al(OH)3 is
subsequently precipitated.

And Al(OH)3 is calcined, Al2O3 is obtained.

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Treatment of Bauxite with NaoH

Bauxite ore is from mine is subjected to size reduction i.e., -100 mesh by jaw crushers and
Hammer mills.

The crushed bauxite is once again ground along with caustic soda in a ball mill to yield a
slurry, which is fed into a digester.

Al203 in the bauxite is dissolved in caustic soda (150-350 g/l Na2O) in the temperature range of
150-220 under the pressure of 5-25 atm.

This treatment dissolves the alumina and leaves the impurities as suspended solids in the
solution

The reactions are as follows:

Al2O3.H20 +2 NaOH = 2NaAlO2+ 2H2O

Al2O3.3H20 +2 NaOH = 2NaAlO2+ 4H2O

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Al2O3.H20 +2 NaOH = 2NaAlO2+ 2H2O

Al2O3.3H20 +2 NaOH = 2NaAlO2+ 4H2O

To dissolve monohydride – temp required is 230 oC and time of 3 hr

Trihydride -- temp required is 180 oC and time is 1 hr.

Since bauxite is a mixture of mono and tri hydrides, a temperature range of 180-230
oC and time period of 2.5 hours is required.

With these conditions, 86-88 % of Alumina in the bauxite is taken into the solution.

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Bayer process
• Alumina (Al2O3) is extracted by digesting crushed bauxite in strong
sodium hydroxide (NaOH) solution at Temp 180-2200C, 5-25atm,
2.5hrs.

• Most of alumina is dissolved to give sodium aluminate (NaAlO2 )

which is soluble in water.

• Insoluble residues or ‘Red mud’, mainly composed of oxide of Fe and

Si, are removed by filtration.

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• In the case of bauxite containing high silica, alumina loss during

the process is increased.
• Silica reacts with NaOH at the first step to give sodium silicate
Na2SiO3.
• Sodium silicate then reacts with sodium aluminate to give
nonsoluble sodium alumosilicate.

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Filtration of Red Mud

Red mud is removed from the solution by --- Liquid from Bayer process is cooled below 100
oC and completely depressurized and taken for settling and clarification section allowed Red
mud to settle in the settling tank.

Addition of Strach speed up the settling of red mud.

Any leftover red mud is eliminated through series of washers where it is confronted with a
counter current flow of hto water.

In the final stage of clarification, the liquor is filtered through a series of filters.

The filtrate obtained is a clear solution of sodium aluminate.

The residue left behind after filtration consists mainly of ferric hydroxide, silica and alumina

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Precipitation of Al(OH)3 and Al203 calcination

Temperature of hot liquor is tapped by heat exchangers for energy conservation and for
cooling the liquor

For filtration, the filtrate is cooled to a temperature below the critical temperature required for
Alumni Precipitation.

Very fine freshly prepared aluminium hydroxide is added to separate from the liquor in a series
of thickeners.

The course Al(OH)3 is calcined in a rotary kiln to produce anhydrous Al2O3

To produce 1 ton of Al2O3 by Bayer process, raw material requirements are

Bauxite – 2.2-2.4 tons
Caustic soda – 0.08 – 0.12 tons
Steam 8-10 tons
Fuel oil – 0.18 to 0.2 tons

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• to decompose NaAlO2 to give alumina (Al2O3),

• The water is then removed by calcining at high

temperatures

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Hall Heroult Process

In 1886, Heroult in France and Hall in the USA independently patented process
of commercial production of Al.

Hall- Heroult process is based on Electrolytic Decomposition of Alumina

dissolved in liquid cryolite

Energy Consumption levels are high in this process.

More suitable in those areas where, electrical energy is available at cheaper

costs.

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Since Alumina is not a ionic compound, a very few ionic melts are capable of
dissolving it to any appreciable extent.
Cryolite (3NaF.AlF3) – a naturally occurring mineral can dissolve up to 15% of
Alumina at 1000 oC
In the present days, Cryolite has been successfully synthesized by passing HF
through sodium Aluminate solution.
HF being produced from naturally occurring CaF2.
The main reactions are:

CaF2(c) + H2SO4 = 2(HF)aq + CaSO4 (c)

(Na2Al2O9)aq + 12 (HF)aq = 2 Na3AlF6 + 6 (H2O)aq

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Small amounts of CaF2 and NaF are added to the cryolite to enhance its
conductivity and to improve the metal recovery.

At 1000 oC, the density of the

molten cryolite is 2.1 g/cm3
that of Al2O3 is 3.96 g/cm3.

When an electrolytic bath contains

10% CaF2 80% Cryolite 5% Al2O3 small amounts of Naf is

electrolyzed , the aluminum liberated (density 2.3 g/cc) is heavier than the bath
and sinks to the bottom.

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Line Diagram of Hall-Heroult process

Constructional Features:
➢ Cell is sunk in the ground with a
top portion of 0.3 m to the
ground level.
➢ Cell is a rectangular steel tank
of 5 m long, 2 m wide and 1 m
deep and lined with refractory.

➢ An iron rod and plate is

embedded in the carbon
mixture.

➢ Tap hole located in the bottom.

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Anode and cathode materials

➢ The cathode lining consists of

refractory lining is faced with carbon
mixed with tar binder situated at the
bottom

➢ Anode may either pre-backed carbon

electrode replaced time to time or
continuous carbon paste where self
back itself. Iron pins are inserted for
electrical contact purpose.

➢ Tap hole located in the bottom.

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Cell Operation: ➢ Cell bath is filled with cryolite, and

anode is lowered into it.

➢ Current is passed through the cell

circuit until the cryolite is completely
melts i.e., around 990 oC.

➢ After complete melting of cryolite,

addition of Al2O3 commences.

➢ Al2O3 decomposes to yield Al and O2

➢ The necessary neat required is

supplied by the resistance of both
electrodes and electrolyte.

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Cross Section electrolysis cell

➢ The reduction cell bottom serves as a cathode, and coal
bars immersed in cryolite serve as anodes
➢ Temperature within the cell is maintained via electrical
resistance.
➢ Oxidation of the carbon anode increases the electrical
efficiency at a cost of consuming the carbon electrodes
and producing carbon dioxide.
➢ solid cryolite is denser than solid aluminium at room
temperature,
➢ liquid aluminium is denser than molten cryolite at
temperatures around 1,000 °C
➢ Aluminium sinks to the bottom of the electrolytic cell
➢ The liquid aluminium is removed from the cell via a
siphon extremely high temperature valves and pumps).

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• Both of the electrodes used in the electrolysis of aluminium oxide are carbon

• Once the refined alumina is dissolved in the electrolyte, it disassociate, and its
ions are free to move around.

• The reaction at the cathode is:

• Al3+ + 3 e− → Al

• Here the aluminium ion is being reduced.

• The aluminium metal then sinks to the bottom and is tapped off, usually cast
into large blocks called Al billets for further processing.

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The cell produces gasses at the anode

➢ At the anode, oxygen is formed:

2 O2− → O2 + 4 e−

➢ The exhaust is primarily CO2 produced from the anode consumption

➢ Hydrogen Flouride (HF) from the cryolite
➢ The gases are either treated or vented into the atmosphere
➢ CO2 involving neutralization of the HF to its sodium salt, to
produce sodium flouride

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➢ Agitation of the bath by CO and CO2 evolution during the

process and magnetic stirring allowed the current flowing
through the bath from cathode to anode, help maintain fresh
addition of Al2O3 in suspension long enough for dissolution in
the electrolyte.

➢ Gases like O2, F and Na releases during the electrolysis

process.

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Decomposition potential of Al2O3 dissolved in Cryolite

Actual Decomposition Potential

In an actual plant operation, the voltage is maintained between 5 V and 7 V.

The breakdown of
voltage requirement is as follows (the values are approximate)
➢ Voltage needed for electrolytic reduction : 1.7
➢ Voltage drop across carbon lining : 0.6 V
➢ Voltage drop due to anode resistance : 0.5 V
➢ Voltage drop due to resistance of electrolyte : 1.8 V
➢ Voltage drop due to contact resistance, leads, and joints : 0.5 V

➢ Total Required Voltage : 5.1

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Anode Effect

Al2O3 content in the bath, in general, is 5-10%.

During the electrolysis process, if the Al2O3 content is decreased below 2%, then
the normal contact between the anode and cathode is interrupted by a gas film
which abruptly increases the resistance.
Because of which normal process gets affected.
This is called Anode Effect.

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Anode Effect
➢ brief upset conditions during the aluminum process.
➢ alumina in the electrolytic bath falls below 2%
➢ the normal contact between the anode and bath is interrupted by forming gas
(Flourine) film, which increases resistance, hence
➢ a rapid voltage requirement increase.
➢ These voltage requirement increases are termed “anode effects” (AEs).
➢ Anode effects reflect an unstable production process and have harmful
environmental consequences by generation of the perfluorocarbons (PFCs) CF4 and
C2F6
➢ the anode effect can be averted by preventing the potential on the anode from
exceeding a critical value to be ~3.5 V vs Al/Al3+
➢ To replace the alumina consumed in the reaction, more alumina must be added

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➢ Under unfavorable conditions, the pots may produce small quantities of the
fluorocarbon compounds CF4 and C2F6, which are known to take part in the
“greenhouse effect” of the upper atmosphere.
➢ However, this emission happens only during the so-called “anode effect,” which
occurs when the alumina concentration drops below a critical threshold (2%).

➢ During the anode effect, the cell voltage climbs from the normal 4.5 volts to over 40
volts.

➢ In modern electrolysis pots, which are fitted with pneumatic alumina transport and
feeding systems, the alumina concentration can be held at an almost constant level.

➢ With the aid of modern, microprocessor-controlled potroom control, the frequency of

anode effects, and hence the emission of fluorocarbons, can be much reduced.
➢ Formerly, about one per day and per cell, anode effects can now be reduced to one
every two months by automated alumina feeding.

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Factors influencing electrolysis

1. Bath Temperature:
Bath temperature is a very important factor. As a rule, increase in the
temperature decreases the current efficiency. (for every one 4 degree raise in
temperature, 1% fall in efficiency). Higher temperature causes more side reactions
and the greater dissolution of the metal in the bath.

2. Higher the current Density, greater the efficiency.

So, current density is to maintain at greater value

3. The lower the density of the bath, the higher the rate of separation of metal
liberated from the bath.
The density can be lowered by using high ratio of AlF3/NaF.
However, usage of high AlF3 has certain drawbacks:
(i) Conductivity of the bath is lowered
(ii) Solubility of Alumina is reduced
(iii) large volume of Flourine is produced
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Factors influencing electrolysis

If NaF is high,
Current Efficiency reduces due to the increase in the concentration of Na ions and
the deposition of Na on the cathode. Na deposition directly reduces the current
efficiency.
4. Current Efficiency depends on Interpolar Distance
Interpolar distance is the distance between bottom of the anode to the top of
the molten bath. .
Current efficiency increases with increasing the interpolar distance and
reaching maximum 90% when the distance is approximately 65 cm.
5. Alumina Content in the bath:
Current efficiency of the bath can be controlled by the amount of Alumina in
the bath. CE is minimum when the Al2O3 content in the bath is 4%.
At values higher or lower than this value, CE is higher.
Generally, for high CE cell should be operated at high conc of Al2O3
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Electrolytic Refining of Aluminium

• Purity of Aluminum produced by Hall-Heroult process is 99.5%

This degree of purity is sufficient for most alloying purposes.

But, for electrical applications and canning, a higher degree of purity is
required.

The purity of the aluminium produced can be improved by electrolytic

refining known as Hoop’s method.
This is a three layer process.

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Refining, HOOPE’S Process

• Top layer pure Al
(density 2.3 gm/cc)
• Middle layer electrolyte
(density 2.8 gm/cc)
• Bottom layer commercial Al or
scrap or Al – Cu alloy of 28-
30% Cu
(density 4.5 gm/cc)
• Three-layer process is not
suitable for Al-Mg alloy scrap,
because Mg reacts with
electrolyte

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Electrolytic Refining of Aluminium

• Electrolytic cell is made of Fe and lined with carbon at the bottom.

Electrolyte composition is :
– 36% AlF3+ 30% Na3AlF6 +18% BaF2 +16% CaF2
• Anode is Graphite electrodes, 950o C
• Aluminum metal produced by the electrolysis of commercially pure
Al.
• contains impurities of Fe, Si and Al2O3.

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Electrolysis
• The lower layer an alloy of impure aluminum with copper (28-30%) serves as
anode.
• The upper layer consists of pure Aluminum and serves as cathode.
• These three layers are separated from each other due to difference in specific
gravity.
• During electrolysis Al+3 ions from the middle layer migrate to the upper layer
where they are reduced to aluminum by gaining 3 electrons
• Equal numbers of Al+3 ions are produced in the lower layer.
• These ions migrate to the middle layer.
• Pure aluminum is tapped off from time to time.
• Hoope’s method gives 99.99% pure aluminum.
• ELECTRO-CHEMICAL CHANGES:
Na3AlF6 ® 3NaF + AlF3 , AlF3 ® Al+3 + 3F-
At the cathode: Al+3 + 3e- ®Al, At the anode: Al ®Al+3 + 3e-
• Overall reaction: Al+3 + Al ®Al + Al+3
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Treatment of Low-Grade Bauxite ores

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Serpeck's process
This process is used when silica is present in considerable amount of bauxite ore

The ore is mixed with coke and heated to 1600o C in presence of Nitrogen, when
aluminium nitride is forms.

Al2O3 + 3C +N2 2AIN + 3C

Silica is reduced to silicon and volatilises off at this temperature

SiO2 +2C Si + 2CO
AIN is hydrolysed with water into aluminium hydroxide at RT

AIN + 3H2O Al (OH)3 + NH4OH

The precipitate is filtered, washed dried and ignited to get Al2O3

2AlN+6H2O = 2NH3 + Al2O3 + 2H2O

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LIME SINTER PROCESS

Lime Sinter Process is suitable for silicious ores such as clay.

Alumina is first liberated by reacting clay (Al2O3.2SiO2) with limestone (CaCO3)

Mix and Sinter

Al2O3 2 SiO2 (C) + 2CaCO3 2CaSiO3 + Al2O3 + 2CO2
1300 – 1400 oC

The reaction products are next separated by leaching the Al2O3 – rich fractions

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Deville Pechiney process

Low grade ores made to react with Na2CO3 in the solid state to produce Solid
NaAlO2
Grind and Sinter
BAUXTIE + Na2CO3 2NaAlO2 + CO2
1000 oC, 2 hr

Al2O3 Filtrate Leach with Hot

Water and filter

➢ The Solid Aluminate is then dissolved in hot water

➢ Al2O3 is recovered as done in the Bayer process.

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Factors influencing electrolysis

➢ Addition of Alumina will be commenced only when the bath attains
molten state (melting point 990OC)
➢ Bath temperature is important and optimum Neither high nor low
➢ Higher current density so greater current efficiency
➢ Lower the density of bath, higher rate of separation (high ratio of NaF
/AlF3 <=3)
➢ Current efficiency related to interpolar distance 65cm (distance from
bottom of anode to top of molten metal bath)
➢ The cell efficiency is high with high alumina content (>4%)
➢ 10% CaF2 + 80% cryolite + 5% Al2O3 + small amount of NaF. Higher the
amount of Al2O3 higher will be the density and sinking of Al is more
difficult

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Bayer process

• Al2O3. H2O + 2NaOH = 2H2O + NaAlO2

• Al2O3. 3H2O + 2NaOH = 4H2O + NaAlO2
• Monohydrate requires 2300C, 3hrs
• Trihydrate requires 1800C, 1hrs
• Bauxite is a mixture of mono and trihydrate so requires 180-2200C, 2.5hrs
• In order to retain water in the liquid state high pressures are applied
• Leachant is cooled to 1000C and settled and redmud is removed
• Starch is added to enhance settling
• Remaining redmud is removed by sending counter current hot water and
finally filtered
• Precipitation add fresh Al(OH)3 removed separated by thickeners

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Extraction of Aluminum

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Bayer’s process -Redmud

• The silica in the bauxite reacts and precipitates from
solution as sodium-aluminum-silicate.
• Iron and titanium oxide and other impurities are not
affected chemically, and being solid, settle out of
solution.
• This waste material, known as red mud, is separated
from the sodium aluminate solution, washed to
recover the caustic soda, and then pumped to
disposal areas
• The disposal of red mud can present an
environmental problem simply because there is so
much of it.

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Bayer’s process -Redmud

• From a few alumina plants, red mud is deposited on
the sea bed under strictly controlled conditions.
• One very common method of disposal is to contain the
mud in an area surrounded by banks.
• After an interval of some years, these ponded areas
can be recultivated to eliminate “visual pollution.”
• Although a great deal of effort has been expended on
finding and developing various uses for red mud, no
bulk application of commercial value has yet been
found

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Factors affecting Bayers Process

• Finer Bauxite, the better the digestion of Alumina in leach solution

• Wet grinding is more preferable for further operations like mixing in leachant

• Combination of temperature and pressure are 180-2200C, 5-25atm, 2.5hrs

• Water is maintained as close to boiling point

• Hot leachant heat is recovered by heat exchangers

• Calcination at 14000C, to decompose Al2O3. H2O and Al2O3. 3H2O it require

12000C and 8000C respectively

• Addition of small amount of CaF2 for better dehydration

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Purification of raw materials

• The material is dissoved in NaOH and heated.
• Al2O3 is selectively dissolved by the reaction
Al2O3 + 6NaOH + 3H2O → 2Na3Al(OH) 6
• Some crystalline forms of SiO2 can also dissolve by the
reaction SiO2 + 4NaOH → Na4SiO4 + 2H2O
• These two new species are soluble,
• Fe2O3 is a basic oxide and hence it is insoluble in this
solution and can be filtered out.
• Na3Al(OH) 6 decomposes to Al(OH)3 (an insoluble species),
which is also filtered out.
• Na3Al(OH) 6 + 2H2O → 3NaOH + Al(OH)3.3H2O
• This is then decomposed by heating to temperatures
above 1000oC to give alumina, Al2O3.
• 2 Al(OH)3.3H2O → Al2O3 + 9H2O

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Reduction of the alumina

• The anhydrous alumina (Al2O3) is dissolved in molten
cryolite (Na3AlF6),
• forming an ionic and electrically conductive solution
• Dissolve upto 15% Alumina at 980-1000o C
• To lower the melting point, cryolite-alumina mixtures also
contain various amounts of other salts, such as aluminum
fluoride (AlF3)
• decomposed by electrolysis, using a consumable carbon
anode with two concurrent reactions
• Al2O3 + 3C → 2Al + 3CO
• 2 Al2O3 + 3C → 4Al + 3CO2
• use of a consumable carbon anode lowers the required
voltage by 1.0 V at the operating temperature of 950-980o C

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Electrolysis
• 1880s, a young American student, Charles Martin Hall, decided
to develop a commercial process for extracting aluminum
using an electric current.
• In his first experiments he electrolyzed solutions of aluminum
salts in water.
• All he managed to produce were the gases hydrogen and
oxygen.
• He tried electrolyzing molten aluminum oxide. It did not work.
• The oxide's high melting point prevented its electrolysis.
• He began a systematic search of different salts for this
purpose.
• In February 1886 Hall passed a direct current through a
solution of alumina dissolved in cryolite (Na3 AIF6) in a carbon
crucible.
• After several hours he allowed the contents to solidify.
• When he broke up the solid he found several small buttons of
aluminum.

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Electrolysis
• Within a few weeks Paul Heroult in France had
independently produced aluminum by an almost identical
process.
• Both Hall and Heroult were only 22 years old.
• Two years later Karl Bayer developed his process for the
extraction of pure aluminum oxide from bauxite.

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Hall-Héroult electrolytic cell

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The electrolysis cell, or “pot

• Steel shell (5m x 2m x 1m) with a lining of fireclay brick for heat insulation,
which is, in turn, lined with carbon bricks to hold the fused salt electrolyte.
• Steel bars carry the electric current through the insulating bricks into the
carbon cathode floor of the cell.
• Carbon anode blocks are suspended on steel rods, and dip into the
electrolyte.
• As the electric current flows through the electrolyte, it melts and by
addition of Alumina

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The electrolysis cell, or “pot

• it breaks down the dissolved alumina into its component elements as
metallic aluminum and oxygen gas.
• The oxygen reacts with the carbon anodes, forming bubbles of CO and
CO2 gas.
• Liquid aluminum settles on the bottom of the cell since it is denser
(specific gravity 2.3 at 960°C) than the electrolyte (specific gravity 2.1).
• Periodically, this aluminum is siphoned off by vacuum into crucibles.
• To replace the alumina consumed in the reaction, more alumina must be
added

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ELECTROLYTIC CELLS

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Charge calculation

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• Agitation of the molten material in the cell

increases its production rate at the expense of
an increase in cryolite impurities in the product.
• Properly designed cells can
leverage magnetohydrodynamic forces induced
by the electrolyzing current to agitate the
electrolyte.
• In non-agitating static pool cells the impurities
either rise to the top of the metallic aluminium,
or else sink to the bottom, leaving high-purity
aluminium in the middle

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Coal anodes
• anode material is consumed in the classical Hall-Héroult reaction
• About 0.5 tons of carbon is used to produce every ton of
aluminum
• compacting blocks from a paste of calcined petroleum coke and
tar pitch
• After this compacting process, the anodes are prebaked in a
calcining furnace at 1120oC
• Instead of prebake anodes, some older smelters use Söderberg
anodes.
• These are continuously formed in-situ by feeding “green” (raw)
paste into the top of a sheet steel shell over the cell.
• Heat from the process bakes the paste to solid anode coke
• Disadvantages of this are: low current efficiency of about 86–
90% (compared with 95% in modern prebake smelters) and more
fume emissions than with prebake anodes

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• Prebaked anodes have to be removed at regular

intervals, when they have reacted down to one
third or one fourth of their original size.
• These remaining anodes are termed as butts and
are usually cleaned outside the cell in a separate
cleaning station to be able to recirculate the
adhering bath materials removed from the cell.
• The cleaned butts are then crushed and used as a
raw material in the manufacturing of new
anodes.
• During anode effect, the bath fails to wet the
carbon anode, and a gas film forms under and
about the anode.
• This film causes a high electrical resistance and
the normal pot voltage, about 4 to 5 volts,
increases 10 to 15 times the normal level.

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Cathode
• The carbon lining which forms the pot cavity
consists of carbon blocks, preformed by external
manufacturers.
• These blocks are placed in the steel pot shell and
cemented together with a paste similar to that
used in making the blocks.
• Thermal insulation consisting of firebrick,
vermiculite, or similar materials is placed
between the cavity lining and the steel shell.
• Carbon pot linings normally last from 4 to 6 years

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Baked anode
compressive strength: 250-300Kg/[Link]
Porosity : 25%

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Pre baked anode Soderberg anode

of calcined petroleum coke and tar pitch some older smelters
Compacting These are continuously formed in-situ by
feeding “green” (raw) paste into the top
of a sheet steel shell over the cell
anodes are prebaked in a calcining Heat from the process bakes the paste to
furnace solid anode coke
compared with 95% in modern prebake low current efficiency of about 86–90%
smelters
less fume emissions fume emissions than with prebake
anodes

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Cryolite
• Chemically it is Na3AlF6, a double
fluoride of sodium and aluminium.
• white granular powder.
• Melting point of cryolite is 990°C.
• Synthetic Cryolite is made from
fluorspar (CaF2), which is found as a
natural mineral.
• Fluorspar is treated with sulphuric
acid to produce hydrofluoric acid HF.
• HF is then reacted with sodium oxide
Na2O and alumina to produce
cryolite

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Electrolyte - Cryolite
• Electrolyte has a number of unique properties, which
make it the only suitable material for the purposes, is
as follows-
• Being molten at a high temperature, which can be
reached without too much difficulty in reduction cells.
• Have a density low enough that it floats on top of
aluminium metal in the cell to prevent the aluminium
from oxidation.
• Used as a solvent for alumina.
• Ionize and conduct electricity so that current can flow.
• Have a low volatility such that losses are not excessive.

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Voltage
• At 4–4.5 volts per cell, the operating voltage is
considerably higher than the theoretical
decomposition voltage of aluminum oxide.
• The difference is due to various voltage losses,
which are unavoidable under industrial
conditions.
• The resulting excess power generates heat,
which maintains electrolyte temperature

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• The individual cells are connected in series,

bringing the supply voltage to over 1000 V,
which is the optimum operating voltage of
thyristor power supplies.
• Thus, a modern potline consists typically of
264 cells in series, supplied at 1150 V.
• Aluminium busbars carry the current from one
cell to the next.

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Methods for Treating Low Grade ores

➢ Bayer process is suitable for high grade Bauxite with low silica content
➢ Bayer process cannot deal with low grade ores or ores with high silica
content

➢ Alternate methods are required for extraction of Al from low grade ores.
➢ Serpeck’s process
➢ Lime Sinter process
➢ Deville Pechiney process

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Serpeck's process
• This process is used when silica is present in considerable amount of bauxite ore.

• The ore is mixed with coke and heated to 1600o C in presence of Nitrogen, when
aluminium nitride is forms.

Al2O3 + 3C +N2 2AIN + 3CO

Silica is reduced to silicon and volatilises off at this temperature

SiO2 +2C Si + 2CO
AIN is hydrolysed with water into aluminium hydroxide at RT

AIN + 3H2O Al (OH)3 + NH4OH

The precipitate is filtered, washed dried and ignited to get Al2O3

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Alternate Route to Electrolysis of Al

Hall-Heroult process was the only commercially available method to extract Al.

Research was carried out using Cl by Amuminum Company of America (AlCOA) and
made available as alternate method as energy efficiency concerned.

• Input Alumina from Bayer’s process

• ALCOA
• TOTH process
• ALCAN

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ALCOA PROCESS
Al2O3 from Bayer process is the input to this process.

Al2O3 is chlorinated under reducing conditions in the presence of carbon at 700-900 oC

Al2O3 (C) + 2C(C) + 3Cl2(g) 2AlCl3(g) + CO (g)+ CO2(g)

The vapours of AlCl3 is separated from the reaction products by condensation at 70 oC

in a fluidized bed containing AlCl3 particles.
All the particles thus formed are continuously fed into the electrolytic cell containing a
fused chloride electrolyte.

The electrolyte is made up of 5 % AlCl3, 50% NaCl and 45 % LiCl is maintained at

700 oC.

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Upon electrolysis by DC current, Liquid Al is

formed at cathode and Cl gas liberated at anode.
The cell in the ALCOA process has a navel design.
It is a bipolar cell consisting of several bipolar
electrodes.
Each bipolar electrode behavies like top as cathode
surface and bottom as anode surface.
A continuous flow of AlCl3 from top to prevent the
molten Aluminum produced upon electrolysis from
forming pools on the electrode.
Arrangements are made to collect the molten Al at
the bottom.

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One Bi-Polar cell is equivalent of 5 conventional

cells.

ALCOA operates at the current densities of 23,000

A/m2 with the electrode gap of 1.3 cm

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Flow Chart ALCOA

Alumina Bayers

Cl
Fluid bed chlorination 700-900oC
Coke

AlCl3(g) ,CO (g),CO2(g)

Fluid bed condensation 70oC CO (g),CO2(g)

AlCl3(g)

Electrolysis 700oC
NaCl,LiCl,AlCl3

Molten Al Cl (g), recycled

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Toth process
A novel process proposed by Toth.

Similar to ALCOA – Alumina from Bayer process is converted to AlCl3 by chlorination in the
presence of Carbon

The formed AlCl3 is reduced by treating with Mn at the temp of 300 oC and a pressure of 15
atm

3 Mn(c) + 8 AlCl3 (l) 3(MnCl2.AlCl3)+2 Al(c)

The AlCl3 dissolved in the liquid Mn is separated by evaporation so as to leave behind solid
MnCl2.
The MnCl2 is oxidized by O2 and 600 oC to produce Mn2O3 from wich Mn needed for the
Toth process, is obtained by carbothermic reduction.
Al produced by this method will have up to 1% Mn.

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ALCAN Process
• Al company of Canada
• Bauxite reduced to Al alloy
• 50%Al + 30%Fe + 10%Si + 5%Ti + 5%C
• Reduction in electric furnace 2000oC / Coke
• Reacted with Preheated AlCl3 at 1300oC
• 2Al+ AlCl3 = 3AlCl at 1300oC
• 2AlCl = 2Al+AlCl3 at 700oC
• Molten Al droplets
• Severe stress corrosion problems affecting reactor of AlCl3

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Bipolar cell

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Bipolar cell, ALCOA

• Several Bipolar cell
• Bipolar electrode like cathode at top and anode at
bottom
• Continuous flow of electrolyte
• Molten Al at the bottom
• Chlorine raised to top and collected
• Chloride electrolyte has higher conductivity
40mohm/cm
• 2.8 mohm/cm of Hall Heroult process
• Distance between electrodes is lower, 1.3cm
• Lowers the energy wasted
• Reduces energy consumption by 30%

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ALUMINIUM PRODUCTION IN INDIA

• BALCO(MP)
• HINDALCO (UP, WB, KERALA)
• NALCO (Orissa)
• MALCO (METTUR)
• HINDALCO – BAYERS PROCESS

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ENVIRONMENTAL PROBLEMS
• HYDROMETALLURGICAL EFFLUENTS OF BAYER
PROCESS
• DISCHARGE OF SODIUM IONS INTO FRESH
WATER (INSTEAD DISCHARGE INTO SEA)
• REDMUD DISPOSE
• HALL –HEROULTS PROCESS
• FUMES OF FLUORIDES, FLUORINE, SODIUM
VAPOUR
• USE ELECTROSTATIC PRECIPITATORS TO COLLECT
FUME AND RECOVER LARGE AMOUNT OF
CRYOLITE

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Fabrication OF Al

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