Week 10 ExctMet-Al

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EXTRACTION OF

ALUMINIUM
PROPERTIES

 the lightest of the common metals


(except with Mg) with density = 2.7
g/cc (1/3 the density of Cu).
 soft and malleable at ordinary
temperature (becomes brittle when
heated to above 150oC).
 silvery white in color
 an amphoteric metal
 good conductor of heat and electricity
 an active metal but it does not corrode
USES
 its chief use is in automobile and aircraft
construction.
 kitchen utensils, aluminum foil and
beverage cans
 high voltage transmission line
 used as solid propellant for rockets
 in the welding of iron and steel.
OCCURENCE
Aluminum is the most abundant and the 3rd
plentiful element on the earth’s crust. The
elemental form does not occur in nature, its
principal ore is bauxite. The major sources of
aluminum are:
 bauxite, Al O .H O
2 3 2

 cryolite, Na3AlF6
 corundum, Al2O3
 orthoclase, KalSi3O8
 beryl, Be3Al2Si6O18
Pohon Industri Alumunium
PRODUCTION PROCESS

Aluminium can be produced via two different


routes: primary aluminium production from ore
and recycling aluminium from process scrap and
used aluminium products.

The production of primary aluminium consists of


three steps: bauxite mining, alumina production
and electrolysis. The last two mentioned will be
described hereafter, bauxite mining is covered in
the section Environment, Ecology & Recycling.
Al PRODUCTION PROCESS
ALUMINIUM PRODUCTION
ALUMINIUM PRODUCTION
ALUMINA PRODUCTION
(BAYER’S PROCESS)
ALUMINA PRODUCTION
ALUMINA PRODUCTION
Bauxite has to be processed into pure aluminium
oxide (alumina) before it can be converted to
aluminium by electrolysis. This is achieved through
the use of the Bayer chemical process in alumina
refineries. The aluminium oxide is released from
the other substances in bauxite in a caustic soda
solution, which is filtered to remove all insoluble
particles. The aluminium hydroxide is then
precipitated from the soda solution, washed and
dried while the soda solution is recycled. After
calcination, the end-product, aluminium oxide
(Al2O3), is a fine grained white powder.
ALUMINA PRODUCTION

Four tonnes of bauxite are required to produce two tonnes of


alumina which in turn produces one tonne of aluminium at the
primary smelter. In 1998, 45 million tonnes of alumina were
produced world-wide. The main production areas are:
Alumina refineries are often located near to bauxite mines for
logistics reasons.
Theoretically, from the stoichiometric equation
(2Al2O3
+ 3C 4 Al + 3CO2), 1.89 kilograms of alumina is
required to produce 1 kilogram of aluminum. In
practice, a very small portion of the alumina supply
is lost and the industry requires approximately 1.93
kilograms of alumina for production of each
kilogram of aluminum.

All commercial alumina is refined from bauxite


using the Bayer refining process. The process,
developed by Karl Bayer in 1888, consists of four
major steps. Bauxite composition varies and
refining plant designs are slightly different to
account for the site-specific quality of the bauxite.
1) Digestion – Crushed, ground, and sized bauxite is
dissolved under pressure with a hot (180°C to 250°C)
sodium hydroxide and sodium carbonate solution in a
series of steam-heated digesters. The concentrations,
temperatures, and pressures employed vary depending on
the properties of the bauxite. Gibbsite is soluble in caustic
soda above 100°C, while böehmite and diaspore are
soluble in caustic soda above 200°C. Since the treatments
of böehmite and diaspore require higher temperatures and
longer digestion times, they are more expensive than
treatment of gibbsite. The aluminum oxides
in the bauxite react to form soluble sodium aluminate or
“green liquor.”
Al2O3•H2O + 2NaOH 2NaAlO2 + 2H2O and
Al2O3•3H2O + 2NaOH 2NaAlO2 + 4H2O
Silicas in the bauxite are detrimental to the
digestion efficiency. They react to form sodium
aluminum silicate, which precipitates. This
precipitate chemically binds the aluminum from the
bauxite and the sodium from the sodium hydroxide
into a solid from which the alumina cannot be
economically recovered. This decreases the yield of
alumina and increases the costs associated with
sodium hydroxide. Chemical additions and the
adjustment of refining practices can effectively
provide desilication and decalcification of specific
alumina streams.
2) Clarification – The green liquor produced by digestion is
clarified to remove sand, undissolved iron oxides, titanium
oxides, silica and other impurities. The insoluble materials,
called “bauxite residue” or “red mud,” are thickened, washed,
and dewatered to recover sodium hydroxide. Bauxite residue
is a large-quantity waste product that is generally stored
adjacent to refinery sites in landfills or lagoons. After
weathering, the landfills can sustain vegetation.
3) Precipitation – The clarified liquid that results from
clarification is cooled and “seeded” with crystals of gibbsite to
aid precipitation of alumina trihydrate (Al2O3•3H2O). This is
the reverse of the digesting step (2NaAlO2+ 4H2O
Al2O3•3H2O + 2NaOH). However, by carefully controlling the
seeding, temperature and cooling rate, specific physical
properties can be given to the precipitating alumina trihydrate.
4) Calcination – Alumina trihydrate is typically calcined in a
fluid bed or rotary kiln at about 980°C to 1,300°C to remove
the water of crystallization and produce the dry white powder,
alumina (Al2O3•3H2O Al2O3 + 3H2O). Calcining rates and
temperatures are carefully controlled and vary depending on
the final physical properties specified for the alumina.
Al PRODUCTION
Al PRODUCTION
Aluminium primary smelting and casting
Primary aluminium is produced in reduction plants (or
"smelters"), where pure aluminium is extracted from
alumina by the Hall-Héroult process. The reduction of
alumina into liquid aluminium is operated at around 950
degrees Celsius in a fluorinated bath under high intensity
electrical current. This process takes place in electrolytic
cells (or "pots"), where carbon cathodes form the bottom
of the pot and act as the negative electrode. Anodes
(positive electrodes) are held at the top of the pot and are
consumed during the process when they react with the
oxygen coming from the alumina.
Al PRODUCTION

There are two types of anodes currently in use. All


potlines built since the early 1970s use the prebake
anode technology, where the anodes, manufactured
from a mixture of petroleum coke and coal tar pitch
(acting as a binder), are ‘pre-baked’ in separate anode
plants. In the Soederberg technology, the
carbonaceous mixture is fed directly into the top part
of the pot, where ‘self-baking’ anodes are produced
using the heat released by the electrolytic process.
Al PRODUCTION

At regular intervals, molten aluminium tapped from the pots is


transported to the cast house where it is alloyed in holding furnaces by
the addition of other metals (according to the user’s needs), cleaned of
oxides and gases, and then cast into ingots. These can take the form of
extrusion billets, for extruded products, or rolling ingots, for rolled
products, depending on the way it is to be further processed.
Aluminium mould castings are produced by foundries which use this
technique to manufacture shaped components.
World-wide trends in production are shown in the following graph.
Aluminium output has increased by a factor of 13 since 1950, making
aluminium the most widely used non-ferrous metal. In 1998, world-wide
production of primary aluminium was about 22.7 million tonnes per year
for and installed capacity of 24.8 million tonnes.
PREPARATION

 Aluminum is usually prepared from bauxite.


 Hall Process reduces bauxite to aluminum.
 The cell contains a series of carbon
(graphite) anodes.
 The cathode is also made of carbon and
constitutes the lining inside the cell.
Al PRODUCTION
Historical Hall-Héroult Energy Utilization
“The first commercial aluminum
cells at Neuhausen, Switzerland
(Héroult) and Pittsburgh,
Pennsylvania (Hall) required more
than 40 kWh/kg of aluminum
produced and had current
efficiencies ranging from 75 percent
to 78 percent.” The Hall-Héroult
process is still electric energy
intensive. Since electricity costs are
an important component (about one
third) of the total production costs,
energy efficiency continues to be a
major area of focus for the
aluminum industry.
HALL PROCESS
Al PRODUCTION
Theoretical Energy for Hall-Héroult Carbon Anode
Reduction
All commercial aluminum production uses a carbon anode
in a Hall-Héroult cell. The carbon is consumed during the
electrolytic process and supplies part of the energy
necessary for the reduction of alumina. This gives the Hall-
Héroult carbon anode process a lower energy requirement
than the direct reduction of alumina to aluminum. The
theoretical energy required for reduction is the same for
prebaked or Söderberg carbon anodes.

The net reaction for the carbon anode Hall-Héroult process is


2Al2O3+3C 4Al+3CO2.
Figure 5.5 shows an idealized Hall-Héroult cell for the
production of aluminum. In this cell, it is assumed that the
reactants (alumina and carbon) enter the cell at 25°C, the carbon
dioxide by product leaves the cell at 25°C, and the aluminum
product leaves as molten metal at the cell operating temperature
of 960°C. The reaction is assumed to occur under perfect
conditions, where there are no reverse reactions, no parasitic
reactions consuming additional anode carbon, no limitations to
the ionic species reacting at the electrodes, and no heat or
energy losses external to the system.
Al PRODUCTION
In actual carbon anode cell operations, current efficiencies
of less than 100 percent result from reverse oxidation
reactions between part of the aluminum metal that is
dissolved in the cryolite and carbon dioxide gas produced
(2Al+3CO2 Al2O3+3CO) and to a lesser extent between
the carbon dioxide gas and the carbon anode (CO2+C
2CO). Current efficiency losses can also result from direct
shorting of the anode to the aluminum pad.

Today’s state-of-the-art reduction cells are achieving


current efficiency levels of more than 96 percent and energy
consumption levels of less than 13.0 kWh/kg of aluminum.
29 The theoretical minimum energy requirement at 100
percent current efficiency is 5.99 kWh/kg of aluminum. The
energy efficiency levels of present state-of-the-art carbon
anode reduction cells are about 46 percent.
Hall-Héroult Reduction Process

A typical modern aluminum electrolysis Hall-Héroult reduction


cell (pot) is a rectangular steel shell 9 m-12 m long, 3 m
4 m wide and 1 m-1.5 m deep (Figure 5.6). It has an inner lining
of carbon, which is surrounded by refractory thermal insulation,
that keeps it isolated thermally and electrically from the steel
shell. Commercial cells range in capacity from 60,000 amperes
to more than 500,000 amperes and can produce more than 450
to 4,000 kilograms of aluminum per day, respectively.
Al PRODUCTION

A cell typically operates at 950°C to 980°C and yields


molten aluminum and carbon dioxide. The molten aluminum
has a higher density than the electrolyte (cryolite bath) and
settles to the bottom of the cell on top of the carbon lining.
Molten aluminum at about 99.7 percent purity is periodically
“tapped” by a vacuum siphon from the cell bottom. The
tapped metal is transferred to holding furnaces where the
metal is alloyed, and entrained gases and impurities are
removed prior to casting. The carbon dioxide and other gases
generated in the cell during the reduction process are
collected and treated to meet environmental regulations.
Al PRODUCTION
Electric current enters the cell through the carbon anode and flows
through 3 cm–6 cm of electrolyte (bath) to the aluminum pad and
carbon lining cathode. The aluminum pad is in intimate contact with
the carbon lining and serves as the charged surface of the cathode.
Steel collector bars are set near the bottom of the carbon lining to
conduct the current to the anode of the next cell.
The 950°C to 980°C molten cryolite and aluminum used in a typical
reduction cell are corrosive. Molten cryolite has low viscosity and
interfacial tension that allows it to easily penetrate any porosity in
the cell lining. To protect the carbon lining, the thermal insulation is
adjusted to provide sufficient heat loss to freeze a protective coating
of the electrolyte, known as “ledge,” on the inner walls. The molten
aluminum pad protects the carbon bottom of the cell. The cell is
never tapped completely dry of molten aluminum. It is essential that
no alumina or frozen ledge form under the metal pad. The carbon
cathode must remain bare for good electrical contact with the
aluminum pad and to minimize wear of the carbon surface.
Al PRODUCTION
Voltage Requirements

The energy consumed in an electrolytic reaction is a function of the voltage


used and the current efficiency of the operating cell (the minimum current is
fixed by Faraday’s Law, see Section 5.3 on page 27). Modern Hall-Héroult
cells operate at high (96+ percent) current efficiencies. The approximate
voltage components of a conventional cell are shown in Figure 5.7.
The electric current flows through the cell and the cell voltage components
can be described as a set of resistors in series.
E = cell reaction + overvoltage + bath + cathode + anode + connectors
Al PRODUCTION
Voltage Requirements
The cell reaction voltage is a function of temperature
and at 960°C, is fixed at 1.2 V(dc).
This is the theoretical minimum voltage required for
the reduction reaction to take place and no cell can
operate at 960°C below this voltage.
The total cell operating voltage includes the addition
of voltages required to overcome the ohmic
resistance of the other cell components.
Alternative Primary Aluminum Processes ???

Secondary Aluminum (Recycling)

Aluminum Processing

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