DATE SUBMITTED: OCTOBER 5, 2012

PRODUCTION OF ALUMINUM BY HALL-HĔROULT PROCESS

ANTE, GRECCO1, LANGCAY, EARL JOHN1, PALACOL, CHRISTJOHN RHOIE1, VERGARA, ANGELICA R. 1
1 DEPT. OF MINING, METALLURGICAL, AND MATERIALS ENGINEERING, COLLEGE OF ENGINEERING

UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES

Aluminum’s extraction and processing involves related operations – bauxite mining, bauxite purification,
extraction of alumina, electrolysis of alumina, and processing. Each step uses its own process, well known are Bayer
Process for bauxite purification and alumina extaction and Hall-Heroult Process for alumina electrolysis.

Bayer Process (Bauxite to Alumina) HALL-HĔROULT PROCESS

In Bayer process, bauxite -- the most
abundant aluminum ore in nature -- is purified to
extract aluminium oxide (Al2O3) or alumina from it.
A. History
Hall-Heroult Process is named after Charles
Hall, an American (23 yrs. old), and Paul Heroult, a
Frenchmen (23 yrs old), who, in 1886, simultaneously
and independently developed the process.

Before 1886, aluminum is as valuable as silver

Figure 1. The Bayer Process
Bauxite is made up of 30-54% aluminum
oxide and the rest are silica, ferric oxide, and titanium
dioxide. We use the Bayer Process to purify the
bauxite. It involves reaction of crashed bauxite with
sodium hydroxide (NaOH), under high pressure and at
170ºC condition, to produce aluminum hydroxide
(Al(OH)3). The Al(OH)3 then precipitates and is heated
to 980 ºC. It decomposes into water vapour and
alumina (Al2O3).
Alumina to Aluminum
The obtained alumina (Al2O3) from the Bayer
Process will then be reduced to aluminum through the
Hall-Heroult Method.
Figure 2. Alumina in its powdered
form and its chemical structure
Basically, Bayer Process is performed to obtain alumina from
bauxite. For this alumina will undergo the Hall Heroult to
produce 99% pure aluminium.
BAUXITE  BAYER PROCESS  ALUMINA
because of its high-cost production but Hall in America
and Heroult in Europe developed a relatively
inexpensive method that is now called Hall-Heroult
Process. This process marked the introduction of
aluminum to wide commercial use.
Furthermore, in 1888, Hall founded
Aluminum Company of America (ALCOA); wherein,
20 years after, had caused a great decrease of Al market
value.
B. Process Components/Set-Up
1. Electrolytes. In Hall-Heroult process, the electrolyte
is a molten cryolite plus dissolved alumina. In Hall and
Heroult times, effeciency problem arose because of
high melting point of alumina, thus it is dissolved in
cryolite. Cryolite is a mineral of aluminum, sodium, and
fluoride in composition. It lowers the melting point of
alumina from 2050ºC to 980 ºC.
Figure 3: Cryolite and
the cryolite-alumina
mixture

ALUMINA  HALL-HĔROULT  ALUMINUM

 Further addition of salts such as aluminum
fluoride (AlF3) and calcium fluoride (CaF2) will
compensate alumina’s high melting point and will The oxygen reacts with the carbon anodes, forming
regulate current efficiency and operation losses. bubbles of CO and CO2 gas. This gases escape the cell
through the cover vent.
2. Electrolytic Cell. The process will take place in a
rectangular steel tank, called electrolytic cell. It has
carbon(graphite) lining that can serve as cathode. An
3O2  1.5 O2 + 6e-
outer iron shell can also be a cathode. While the anode
is the set of thick carbon blocks suspended with steel
rods from the top.

C + 2O  CO2

Figure 4. The Electrolytic Set-up Figure 6. Reaction at the Anodes

Anodes support is adjustable so it can be Aluminum ions are attracted to the negative
lowered down when it is consumed during process. graphite lining.
Moreover, the cell’s cover has a vent for fumes. 2Al3+ + 6e-  2Al
3. Cell’s Power and Temperature Requirement. An
operating voltage of 4-5 volts and direct current of
50000-300000 amperes are required to run the
electrolytic cell; while the temperature needs to be
maintained between 950 ºC -1050 ºC to avoid
Figure 7. Reaction at the cathode
solidification in electrolytes.
Meanwhile, liquid aluminium settles on the
C. Input/Output
bottom of the cell since it is denser than the electrolyte.
For every 1000 kg of aluminum produced, the The aluminum is periodically tapped off at the bottom
process consumes 4000 kg of bauxite (equivalent to of the cell.
2000 kg of alumina after Bayer process), 70 kg of
When electric current is passed, the
cryolite and 5-10 kg of other salts, 450 kg of Carbon
aluminium ions from the middle layer of liquid move to
for anodes, and 5.6 x 109 J of energy.
the top layer and are discharged at the cathode as pure
D. Electrolytic Reduction aluminium. Aluminium
formed at cathode gets
Its objective is to reduce aluminium ions to collected at the bottom of
form aluminum metal (at the cathode). the electrolytic cell. The
metal obtained by this
As 50000-300000 amperes of electric current method is about 99% pure.
flows through the electrolyte, it breaks down the Figure 8. The Layers of electrolyte
dissolved alumina (Al2O3) into its component elements: when passed by electric current.
metallic aluminum (Al3+) and oxygen gas (O2-). Figure 9. Collection of Aluminum
At the same time,
Al2O3  2Al3+ + 3O2- an equivalent amount of
aluminum from the bottom
Figure 5. Reduction of (Al2O3)
layer of liquid migrates to
the middle layer leaving
behind the impurities. The
pure aluminum is removed from the tapping hole from
time to time.
The carbon anodes, on the
other hand, are being
consumed during the process
as O2- ion reacts with its
Figure 10. Consumption of C ions forming CO or CO2.
Carbon Anodes
Thus from time to time, the carbon blocks
can be lowered further into the electrolytes, and when
totally consumed are being replaced for almost every 2
weeks.
When the theoretical amount of aluminum is
produced, more alumina is added into the cell as Hall-
Heroult is a continuous process.
E. Development. Thru time, two primary aluminum
technologies use Hall-Heroult process, the Soderberg
method and prebake method.
Figure 11. Soderberg and Prebake Method
Some smelters use carbon anode blacks that
are continuously baked “in-cell”, this is the Soderberg
method. The heat produced from the electrolysis
bakes the carbon anode as it moves down the cell.
Thus, carbon anode paste is just continuously
replenished at the top of the cell. But this method emits
a significant amount of fumes that is a health hazard
for the workers and has lower current efficiency
relative to the prebake method.
Prebake method forms the carbon anodes in
ovens outside the reduction cell. The fully formed
anodes are just inserted into the molten aluminum in
the smelting pot for further alumina reduction.
Industry favors prebake method and thus it is the one
used in all aluminum smelter today.
F. Other known electrolysis process. On 1976,
Alcoa had a test operation using aluminum chloride
electrolysis because its projected capacity is 15,000
ton/year, much larger than the Hall-Heroult
production.
It has more power efficiency by saving 30%
of electric power consumption and it avoided fluoride
emissions and made more optimum used of anode.
Though after some operations, the aluminum
chloride electrolysis was shut down due to excessive
cost of producing anhydrous aluminum chloride
feedstock. Its success remains uncertain for economics
of producing aluminum chloride feedstock remain
unclear. Thus the aluminum industry has continued to
use Hall-Heroult process.
REFERENCES
[1] http://ibchem.com/IB/ibnotes/full/ope_htm/hall_cell.htm
[2] http://en.wikipedia.org/wiki/Hall%E2%80%93H%C3%A9roult_process
[3] http://www.elmhurst.edu/~chm/vchembook/327aluminum.html
[4] http://www.propertiesofmatter.si.edu/Extracting_aluminum.html
[5] http://sam.davyson.com/as/physics/aluminium/siteus/extraction.html
[6] http://entrancechemistry.blogspot.com/2011/05/extraction-of-
aluminium-from-bauxite.html
[7] http://inventors.about.com/library/inventors/blaluminum.htm
[8] Animation: Electrolysis-Extraction of Aluminum in alumina in the
Hall-Heroult Cell (from www.flashscience.co.uk)
[9] www.tms.org/pubs/books/4062.chapter2.pdf
[10] courses.chem.psu.edu/Chem112/Spring/ajbnotes/24_metallurgy.pdf
[11]http://www.heattreatconsortium.com/MetalsAdvisor/aluminum/process_
descriptions/anode_baking.htm
PHOTO CREDITS
Figure1: snapshots from Aluminium from bauxite in 1-30
(http://www.youtube.com/watch?v=Pur6vDbPb_I)
Figure 2: alumina frompcykj.com
Figure 3: Cryolite from webmineral.com
Figure 5,6,7,9,10: snapshots from Electrolysis-Extraction of
Aluminum in alumina in the Hall-Heroult Cell
(www.youtube.com/watch?v=G0czuF4gEDE)
Figure 11:
http://www.heattreatconsortium.com/MetalsAdvisor/aluminum/pr
ocess_descriptions/anode_baking.htm