PROPERTIES OF ALUMINA IN

SMELTING
 Types of aluminium reduction cell

• Prebaked
• Soderberg
 Soderberg type cell

+ + Stud
Frozen bath
or side Gas hood
freeze Alumina
powder
Anode
Carbon side
Electrolyte wall
Carbon
Molten aluminium bottom block

Cathode Collector bar

Steel shell
Refractory
 Prebaked type cell
Alumina

Busbar
Alumina layer
Cover

Collector bar Stud

Anode Anode Electrolyte
Metal
Side ledge Cathode
block
 Sodarberg and prabked anode
• Prebaked and soderberg anode contain same
ingredient i.e. petroleum coke and coal tar pitch.
• In Prebaked anode the petroleum coke and coal tar
pitch are moulded into blocks and baked in a
separate anode baking furnace at 11200 c
• Prebaked anode are removed regular interval usually
after 22 days
• The most advantage of sodarberg anode there is no
need of baked plant
• For Sodarberg pitch the maximum paralysis
temperature is 9500c and anode paste has a high
pitch content.
• Carbon density is usallually lower as compared to
prebaked anode
 Basics of electrolysis

  Electric current outside the cell in metallic conductors like bus,

collector bar, electrodes etc. flows by movement of electrons and
the conduction is called electronic conduction
  Current flows through electrolyte by movement of ions and is
called ionic conduction
  This change from electronic conduction in the bus and electrodes
to ionic conduction in the bath requires chemical reaction to take
place at electrodes for flow of current
  Ions with positive charge are attracted to the cathode and are
called cations
  Ions with a negative charge are attracted towards anode and are
called anions
  At the cathode, electrons reacts to discharge positive ions and
produce a reduced product - reduction process
  At the anode electrons are extracted either by discharging
negative ions to form oxidised product or by forming positive ions
- oxidation process
  The bottom carbon line of the cell is often called cathode, the
true cathode is the surface of the molten aluminium (this bottom
must remain bare to provide electrical contact to molten
aluminium)
  Oxygen of the dissolved alumina is discharged and consumes the
carbon anodes in the cell. This oxide ions comes from the alumina
complex ions in the bath, which are formed on alumina dissolution
in the bath
  The frozen ledge thermally and electrically insulates the walls
preventing their acting as cathodes and being eroded by formation
of aluminium carbide that subsequently would dissolve in the
molten electrolyte and be oxidised. The ledge also serves to
stabilise the temperature of the bath by freezing to a greater, when
heat generation is low and thinning when heat generation
increases
 Introduction
Introduction

In aluminium smelters alumina serves the following function :

Raw material for production of metallic aluminium
Thermal insulator
Prevents air burn of carbon anodes
Absorbent for gaseous fluoride emission
 Alumina added to cell

Dissolved in electrolyte

Crust
Al2O3
At Aluminium/Bath
interface
Bottom sludge
 Alumina added to cell

 Alumina is not dissolving efficiently (and hence forming sludge ) is

cause of many of the operating problem.
 Alumina is added in a batch wise manner
 Powdered alumina is dropped from a feeding system
 The feeding operation should avoid or minimize the formation of
sludge which is accumulation of undissolved oxide electrolytes that
rests on the cathode lining
 The excessive amount of sludge changes the anode effect frequency
and also unsettle the metal pad
 Types of alumina

Broadly speaking there are two types

of alumina :

– Sandy

– Floury
Comparison of properties of Sandy and Floury Alumina

Property Sandy Floury

Temperature of calcination Low temperature High temperature
α-Content 2-25 % 75-90
Loss on Ignition 0.8-3.0 0.2
BET Surface Area 30-80 m2/gm 25 m2/gm
Fine Fractions < -45 Micron 4-20 % 20-50 %
Bulk Density 0.9-1.1 gm/cm3 0.8-0.9 gm/cm3
Angle of repose ( flowability) 30-34o (Better ) > 40o ( Poor )
Crystal Size Coarser Smaller
Settling rate in bath low high
Tendency in Bath Form Agglomerate Form Sludge
 ALUMINA PROPERTIES
-SMELTER POINT OF VIEW-
 Chemical purity
•This refers to the content of impurity oxides in the
alumina
•Importance - cell performance and metal purity
–Major impurity is sodium oxide (0.5 to 0.6 mass%)
Role - Reacts with AlF3 in bath to form cryolite and
accounts for net consumption of AlF3
– 3Na2O + 2AlF3  6NaF + Al2O3
–Calcium oxide (<0.06 mass %)
Role - source of CaF2 (3 to 7 mass %) in the bath
–Other minor impurities are silica, titania and iron
oxide, and in addition the oxides of phosphorous and
vanadium
 Alumina impurities -1

METALLIC IMPURITIES
• All impurities in alumina dissolve in molten cryolite by
reaction with it to form the equivalent fluoride and oxy-
fluoride complex
• The impurities which can be reduced by aluminium get
reduced either electrochemically or chemically reduced at
metal / electrolyte interface.
• These reaction apply to all metal impurities except the
alkali and alkali earth group (Lithium, Sodium, calcium,
barium and magnesium)
 Alumina impurities -2

MULTIVALENCE IMPURITIES
• The multiple valence reducible impurities such as vanadium,
Phosphorous are considered to impose secondary problems
• They are partially reduced by dissolve metal away from metal
/ electrolyte interface. These partially reduced ionic species
are taken back to anode due to bath circulation get
reoxidised in bath.
• In Bath : V3+ + Al( Diss)  V + Al3+
• At Anode : V  V3+ + 3e-
• Thus they contribute to a cyclic process of lowering the
current efficiency.
• The extent of the lowering of efficiency is dependant on
steady state concentration of the species in the bath which in
turn, is proportional to the impurity content in the alumina.
 Alumina impurities -3

ALKALI AND ALKALI EARTH GROUP

• For metallic oxide impurity in the which is an alkali
or alkali earth group such as calcium, magnesium
and barium the effect of each impurities shifts an
emphasis on aluminium fluoride consumption.
• This group is not chemically or electrochemically
reduced since it is more stable than solvated AlF3.
However, they also make bath more alkaline. Thus
additional AlF3 is required to neutralise the alkali
fluoride and also adjust the fluoride or bath ratio
down to the operating level.
 Alpha alumina content

• Crystallographic form of alumina formed at 1250°C

calcination temperature
• Typical alpha content range 5 - 80 mass%.
• Significance of the alpha content is related to the
crust formation along with it’s hardness, density and
thermal conductivity
• Low alpha alumina is preferred for the reason that it
requires less heat of dissolution
• Preferable 10-30 mass % in order to obtain the best
crust quality
 Angle of repose

• Constant angle to horizontal by cone - pile of

alumina powder
• Factors
– Shape of the grains
– Grain size distribution
• Typical values for sandy alumina ranges from 30
to 36°, while for floury alumina it is greater than
40°. Low values are preferable
Angle of Repose
Instrument
 Angle
Angle of
of Repose
Repose

r = h cot ө + d / 2
Where h = height of the funnel outlet
above the centre of the card
d = diameter of the funnel outlet
r = radius , shown in concentric circles
ө = angle of repose
 BET Surface area

• A crystal inter-granular network is formed and

restructured after the calcination in the Bayer
process, this porous network area is known as
BET surface area
• BET surface area effects the following in
reduction process :
– Rate of dissolution of the alumina in the bath
– The ability of the alumina to absorb and react with
hydrogen fluoride and sulphur dioxide
– For floury it is < 5m2g-1 and for sandy alumina it ranges
from 80-100m2g-1
 Density

Real density Bulk density

• Measured after the • Measured by filling
alumina is finely grounded vertical cylinder with
below 10m alumina
• Ranges 0.90 to 1.15
• Ranges from 3.45 to 3.60 kgdm-3
kgdm-3
• Alumina feeders in the cell
• Highly dense alumina measure the alumina
tends to settle earlier to dumps in volume, any
the cell bottom increasing variation in the bulk
the risk of sludge density may cause
formation inconsistencies in the
weight of alumina added
to the cell
 Loss on ignition (LOI)

• Loss on ignition is the weight loss of the alumina

on heating between specified temperatures i.e.
300 to 1100°C in an inert atmosphere. It is
qualitative indication of degree of Calcination
• Range 0.5 % - 0.9 %.
• Low value are preferred to avoid fluoride
emissions through hydrolysis
 Particle size distribution

• The normal grain size of alumina ranges in between 20 to

150 m
• The proportion of large particles are limited to have high
rate of dissolution
• Small particles called fines are also limited due to dusting
emissions and mechanical handling problems
• Particle size distribution is as follows :
– Coarse fraction < 15 % [retained on +100m screen]
– Fine fraction < 20 % [less than +45m]
– Super fines < 0.8 % [less than +20m]
 Flow funnel time

• Time required for alumina to flow through funnel of

said dimension and under specified conditions
• Ranges from 4 to 7 minutes per 100 g of alumina
• Short funnel time preferred for high dissolution rate of
alumina in bath
• Longer funnel time results in inconsistent alumina
flow which has greater tendency to form lumps on the
surface of the bath before dissolution
 Alumina dissolution
Alumina Dissolution

Effective dissolution is a decisive factor for stable operation

Sludge formation is unfavourable due to :
Disrupts the current path
Lowers current efficiency
Disturbs the control strategy in the sense that alumina
content in the bath fluctuate
Large variation in alumina concentration can lead to anode
effects
For best results, the alumina dispersion should be rapid, this
relates to optimisation of alumina feeding and alumina properties
 Dissolution process consists of

• The cold alumina hits the surface of bath and spreads on it

• The dissolution process starts as soon as the alumina grains are
exposed to bath
• Grains are encapsulated in frozen bath
• Float on the bath surface upon addition - raft
• Gamma phase transforms to alpha phase
• Formation of bath / alumina agglomerates grains and big
agglomerates sink to bottom of the cell
• Shattering of particles into fines fragments
• Dispersion through bath gradually as particles and
agglomerates
• Re-melting of frozen bath
• Dissolution into the bulk bath
 Properties effecting dissolution

• Operating variables
• Bath composition
• Alumina quality
 Alumina quality for dissolution

• Alpha content
• Particle size distribution
• Flow funnel time
• Loss on ignition
 Alumina dissolution problem indicators

• Changes in sludge level and metal height

• Cell temperature variation

• An apparent increase in current efficiency

 Heat of dissolution

Continuous feeding Batch feeding

• Rate of dissolution is • Rate of alumina
close to rate of dissolution is very
addition for the slow due to raft
reason that alumina formation on bath
gets dispersed and surface and large
dissolved quickly agglomerates within
• System recovers melt
quickly after feeding • System takes long to
is stopped recover after feeding
is stopped
 Effect of alumina properties on alumina
dissolution rate

Properties Effect on dissolution rate

• Particle size • Decreases with increase in
particle size

• Decreases with increase

• LOI LOI upto 1.5 mass %

• Flow funnel time • Decreases with decreasing

flow funnel time
 Dissolution rate

• In order to have high dissolution rate,

one should have :

– large bath/alumina contact area

– Low rate of agglomeration

– High rate of disintegration of agglomeration

 Ranking of alumina properties

1. -20 micron content • 13

2. -325 mesh content • 10
3. Angle of repose • 9
4. Moisture content • 9
5. Flow funnel reading • 9
6. Attrition index • 7
7. LOI • 6
8. Sodium content • 5
 Ranking of alumina properties

9. BET surface area • 5

10. Gibbsite content • 5
11. Calcium content • 4
12. Bulk density • 4
13. +100 mesh particles • 3
14. Contents of Fe, Si, Li & P • 1
 Attrition index

• Measure of the strength of the agglomerated grains

of the alumina to withstand mechanical handling and
transport without being crushed into finer particles.
• Importance in case of dry scrubbing systems. The
agglomeration of particles should withstand the
mechanical handling and impaction in dry scrubbers
without producing an excess proportion of the -45 m
powder
• Maximum is usually 10, while 5 is a more preferable
value for the attrition index referring to the -45 m
fraction
 Quality checks of alumina

• Quality checks that can reduce the likelihood of alumina

dissolution problems

– Measuring flow funnel time / flowability of alumina

– Monitoring the particle size distribution of alumina

being fed to the cell (especially in the fine function)

– Determining the volatile content of alumina