Alumina Technology

R.N.Goyal
JNARDDC, Nagpur

1. Introduction

Commercially alumina is produced from bauxite by age old Bayer process. It

consists of following main processes:
! Desilication
! Digestion
! Precipitation

2. Desilication
In the Bayer process the desilication of bauxite is an important step to maintain
the alumina quality. It requires conversion of reactive silica of the bauxite into a
non-soluble sodalite complex (Sodium aluminium silicate or sodalite). The
desilication can be carried out before digestion or after the digestion process. If
the desilication is carried out before digestion it is termed as pre-desilication
whereas if the desilication follows after digestion, it is termed as post desilication.
The advantage of pre-desilication is that there is no risk of auto-precipitation
occurring during the post desilication process and overall energy requirement in
the pre-desilication is lower as compared to post-desilication.

2.1 Pre-desilication
During desilication the caustic soda reacts with the kaolinitic portion of the
bauxite forming sodium silicate. Apart from this the caustic soda also reacts with
the gibbsite to form sodium aluminate which further reacts with sodium silicate to
form sodium aluminosilicate complex having the structure as x Na2O. y Al2O3. z
SiO2. n H2O. This complex is solid in nature and goes along with the red mud
thus desilicating the bauxite with respect to silica content. The values of x, y, z
and n of the sodalite complex varies from plant to plant depending on the bauxite
characteristic and the digestion parameters. The major reactions occurring during
desilication are as follows:
Na2O + SiO2 = Na2SiO3 ------ (1)
Na2O + Al2O3 = 2NaAlO2 ------ (2)
Na2SiO3 + NaAlO2 = x Na2O y Al2O3 z SiO2 n H2O ------ (3)
The desilication reaction is thus a consecutive reaction in which the reaction can
be represented as :
A (Kaolinitic silica) → B (sodium silicate) → C (Sodalite complex)
In this reaction the rate constant k1 for A → B is higher than the second reaction
rate constant k2 for B → C. The dissolution of kaolinitic silica is dependent on
temperature and caustic concentration. Higher the temperature and caustic
concentration, higher is the silica dissolution resulting in increase in silica level in
the liquor. The second reaction rate constant is lower as compared to the first
reaction requiring in an increased retention time for the second step. The reaction
proceeds faster in presence of seed of sodalite. Desilication reaction is
proportional to the reactive silica content of the bauxite. Higher the silica content,
higher is the driving force of this reaction. Due to this reason, it is difficult to get
satisfactory desilication when the silica content in the bauxite is lower than 1-1.5
%. Desilication rate constant varies depending on temperature, holding time,
bauxite solids concentration, and caustic and alumina concentration of digestion
liquor.

2.2 Factors Affecting Desilication

2.2.1 Temperature

Higher the temperature faster is the rate of desilication. If the temperature is

further raised beyond the critical temperature, the sodalite complex undergoes
dissolution and proceeds faster than the desilication, with the result that the silica
concentration of the final liquor becomes high. So as to bring down the silica
concentration in the liquor to a lower level, temperature lower than the critical

V ariatio n of S ilica C o ncen tration w ith

T em p eratu re at 800 g p l b au xite

3
Silica Conc., gpl

2 .5
90 °C
2
95 °C
1 .5
10 0°C
1
0 .5
0 1 2 3 4 5 6 7 8 9 10
T im e , Hrs.

temperatures need to be maintained. A temperature above critical temperature

results in poor desilication output. Also at higher temperature the equilibrium
concentration of the silica in the liquor is high. Normally plant prefers to carry out
desilication at temperature ranging from 90 to 100oC.

2.2.2 Effect of Bauxite Solid Concentration

The higher solids concentration of bauxite promotes higher desilication. A change

of solids concentration from 200 gpl to 800 gpl can sensibly reduce the silica level
in the liquor at a lesser residence time. The reason for the same is that the higher
bauxite solids concentration in the slurry would yield more desilication product
seed, which could in turn accelerate the desilication process. Nowadays with the
current technological advances, it is possible to pump and agitate slurry with
solids concentration up to 800 - 1000 gpl. The effect of bauxite solids
concentration on silica concentration in the liquor at various residence time is
shown below

Variation of Silica concentration in liquor at different

bauxite solids concentration at 90°C
2.5
Silica Conc., gpl

2 200 gpl
300 gpl
1.5
400 gpl
1 500 gpl
0.5 600 gpl
800 gpl
0
1000 gpl
0 1 2 3 4 5 6 7 8 9 10
Time, Hrs

2.2.3 Caustic Concentration of Liquor

Higher the caustic concentration faster will be the dissolution of reactive silica
from bauxite in the liquor. But at the same time high concentration of caustic
liquor will have a higher equilibrium concentration of the silica lowering the
desilication rate.

2.2.4 Alumina Concentration of the Liquor

It is quite clear that for the second step, the dissolved silica reacts with alumina to
form sodalite complex. During desilication step some dissolution of alumina also
occurs. It is observed that desilication rate is better when the starting
concentration of the alumina is low. The higher alumina concentration in the
solution reduces the degree of silica supersaturation, with the result reducing
driving force for the desilication reaction.

2.2.5 Residence Time

The residence time required for desilication varies with the silica content of the
bauxite and solids concentration. If the silica content of the bauxite is low then
appreciable desilication output is not achieved in 8-10 hours and hence it
becomes necessary to continue desilication up to 16 hours. The retention time for
desilication can be reduced for achieving the same silica concentration in the
liquor by increasing the bauxite solids concentration.
2.3 Post-desilication

In some plant post-desilication is practiced after digestion and after adding

dilution liquor to reduce the silica concentration in the feed to settler. Post-
desilication step has its own disadvantages. In post-desilication slurry volume
increases due to addition of dilution liquor, which is necessary to avoid auto-
precipitation during the post-desilication step. Because of this the energy required
increases and at the same time during post-desilication step, the auto-
precipitation losses are higher resulting in net reduction in extraction efficiency.

3. Digestion Process
Presently three digestion technologies are being employed through out the world.
These are
# Atmospheric Digestion
# Low Pressure Digestion
# High Temperature Digestion
Bauxite is digested at temperatures ranging between 105°- 260 °C with caustic
soda concentration varying from 165 to 220 gpl as Na2O depending upon
quality/mineralogy of the bauxite. Super saturation attainable for solubility of
gibbsite at various caustic concentrations and temperatures is shown in the figure
below.
Gibbsite solubility data in caustic liquors

400
350 250 gpl
Alumina conc. (gpl)

300
200 gpl
250
200 150 gpl

150
100 gpl
100
50
0
40 60 80 100 120 140 160

Temperature ( o C )

From the solubility data of the gibbsite, it is possible to attain a RP of 1.40 at

140oC with 200 gpl Na2O caustic concentration whereas at atmospheric pressure
digestion (107oC) with Na2O concentration of 200 gpl caustic concentration the
achievable RP is 1.12. The monohydrate bauxite contains mostly boehmite and
diaspore. The boehmite requires relatively higher caustic concentration and
temperature for its extraction. For bauxite containing higher content of boehmite,
it requires temperature in the vicinity of 200 – 240oC for economical extraction of
alumina. Most of central Indian bauxite deposits contain higher content of
boehmite and hence plant operating with these deposits like BALCO and
HINDALCO operate at a temperature of 240oC. The equilibrium solubility curve of
boehmite dissolution at various caustic concentration and temperatures is shown
in the figure given below: Usually a higher residence time is given in the plant to
obtain alumina concentration near equilibrium.
Boehmite solubility data in caustic liquors

350

300
Alumina conc. (gpl)

250 250 gpl

200 200 gpl

150 gpl
150
100 gpl
100

50

0
60 80 100 120 140 160 180 200 220 240 260 280

Temperature, o C

From the boehmite solubility data, it is possible to attain an RP of 1.1 – 1.28 at a

Na2O concentration of 150 gpl in the temperature range of 220 – 260oC. Similarly
with a caustic concentration of 200 gpl as Na2O and above temperature range it
is possible to attain a RP of 1.13 – 1.30.

3.1 Atmospheric Digestion

The atmospheric digestion process, developed by Aluminium Pechiney (France)
ensures lower reactivity of silica, uses low digestion temperature (105°-108°C).
Atmospheric pressure digestion because of its extreme simplicity presents many
operational advantages:
• Higher plant operating factor
• Less digestion maintenance and cleaning costs
• No pressure safety specific problems
• No wear problems during digestion and flashing etc.
This technology is in operation in two plants namely NALCO and Guinea.
However it has the following disadvantages: -
• During atmospheric digestion, part of the well crystalline gibbsite remains
undigested causing lower digestion efficiency and higher bauxite
consumption.
• The undigested gibbsite grains further acts as seed to enhance the hydrolysis
loss of alumina in the post desilication and settling step.
• Due to atmospheric digestion, the supersaturation of the digested liquor
cannot be increased to a desired level causing lower liquor productivity.
• Raw material consumption including energy is higher resulting in higher cost
of production.

3.2 Variation of Digestion Efficiency With Holding Time at Atmospheric

Pressure Digestion

The digestion studies carried out at JNARDDC for east coast bauxite at 106oC
temperature and 210 gpl Na2O caustic concentration at various residence time
indicates that the digestion efficiency increases upto 60 minutes holding time and
beyond that there is no appreciable change.

Digestion Efficiency v/s Holding Time at Atmospheric Pressure

(106°C) and at 210 gpl Na2O & 1.1 RP

95
Digestion efficiency, %

93

91

89

87

85
0 30 60 90 120 150
Holding Time, minutes

3.3 Low Pressure Digestion

Low pressure digestion is more suitable for gibbsitic bauxite and is being
employed for alumina production in most of the plants in the world. Generally
bauxite slurry after desilication is mixed with digestion liquor and this thin slurry is
heated in single tube/multi-tube single pass or multi-tube multi-pass tubular
heaters and finally pumped to the autoclave where live steam is fed to maintain
the desired temperature. This system not only facilitate better heat recovery but
also avoids caustic embitterment of carbon steel material of tanks and pipe lines
by complexing of hydroxyl ions with dissolved alumina to form aluminate ions.
The liquor to bauxite charge is a tricky situation in Bayer process. If the liquor
quantity is less as compared to bauxite charge then higher super saturation is
achieved but at the expense of lower digestion efficiency. On the contrary if the
liquor quantity is higher than the desired, the super saturation achieved is less
but the digestion efficiency is higher. Therefore it is essential to determine the
optimum conditions at which both digestion efficiency and super saturation will be
high.
The required concentration of digestion liquor and temperature for digestion is
usually decided on the basis of chemical and mineralogical analysis of bauxite.
Low pressure digestion technology is applicable for those bauxite in which there
is appreciable quantity of gibbsite and low quantity of boehmite.
Low temperature digestion is carried out at elevated temperature ranging from
120 -180oC with caustic concentration ranging from 150 –220 gpl as Na2O. The
only problem associated with extraction at higher temperature is boehmite
reversion, which usually reduces the extraction. However it can be reduced by
addition of lime during digestion. The experiments conducted at JNARDDC for
low pressure digestion of east coast bauxite at different temperature indicates
that as the temperature increases the digestion efficiency increases but after
160oC temperature there is a drop in digestion efficiency.
Low Pressure Digestion
Digestion Efficiency v/s Temperature
at 180gpl Na2O, 1.1 RP, 30min. Res. time
Digestion efficiency, %

90

80

70
100 120 140 160 180 200
Temperature° C

3.4 Benefits of Low Pressure Digestion Over Atmospheric Pressure

Digestion
The benefits in low pressure digestion are as follow as: -
# Higher extractability as compared to atmospheric pressure digestion
leading to low bauxite consumption and less generation of red mud.
# Higher super saturation of aluminate liquor in comparison to atmospheric
digestion leading to higher liquor productivity
# Flashing of digested slurry will result in recovery of valuable flash steam,
which can be used in desilication or evaporation.
# Flashing of steam will reduce the evaporation load.
# The alkaline condensate obtained from flashed steam can be used for red
mud washing or for product hydrate washing.
 Comparison of Low Pressure and Atmospheric
Pressure Digestion of Gibbsite in Plant liquor

1.7
RP (Alumina/Caustic)

107°C
1.5
1.3 140°C

1.1
0.9
0.7
50 100 150 200 250 300 350
Caustic conc. (Na2O) gpl

3.5 High Temperature Digestion

High temperature digestion technology is useful for mostly gibbsitic and boehmitic
mixed bauxite in which the percentage of boehmite is higher i.e. 8-10 %. The
alumogoethite present in bauxite, which creates problem during settling, can also
be extracted at high temperature with addition of lime as additive. For dissolving
diasporic bauxite, high-pressure technology is adopted in which a temperature
upto 260-280oC is required with lime as an additive upto 3 % by weight of
bauxite. In Indian aluminium industry only BALCO and HINDALCO are operating
at high temperature digestion i.e. at 240oC.

3.5.1 Advantages of High Temperature Digestion

# High temperature digestion is able to digest most of the boehmite content
of the bauxite.
# High temperature digestion helps in extraction of large quantity of flashed
steam, which helps in reducing steam consumption as the flashed steam
is reutilized in the process for heating the slurry.
# Removal of flashed steam helps in reducing overall evaporation load in the
Bayer process.
# High temperature digested mud is more crystalline and hence it has better
settling characteristic, requiring less quantity of starch or synthetic
flocculant.
# It is possible to achieve higher super saturation in the aluminate liquor,
resulting in higher liquor productivity.
4. Red Mud Settling
The solid waste from the digestion process known as bauxite residue or red mud
is required to be separated from the pregnant liquor containing sodium aluminate
as quick as possible in order to reduce the hydrolysis loss of alumina (back
reaction) with the red mud and also reduce the impurities entering the
precipitation circuit. This is generally accomplished in large diameter conical or
flat-bottomed tanks fixed with slow speed rakes. The digested slurry is usually
diluted to appropriate concentrations with the first washer overflow or appropriate
liquor to achieve reasonable settling rates. Red mud separation is tedious and
time-consuming process and hence to enhance the rate either natural flocculants
such as starch, rice bran etc. or synthetic flocculants which are either water
soluble high molecular weight polyacrylates or the hydroxamated
polyacrylamides are used. In the initial years only the natural flocculants were
used. However because of the increased plant capacities, more stringent product
granulometry and high productivity it has become essential to replace the natural
flocculants which add up organic contaminants to the system and makes it almost
impossible to control with the synthetic flocculants. However almost all the plants
which use the synthetic flocculant use it in combination with the natural flocculant
so as to get faster settling rate and also better overflow clarity.
Settling tanks are generally of 3000 – 6000 m3 capacity depending on the settling
rate of the mud and plant capacity with huge inbuilt rakes. Generally overflow
clarities of 0.1 – 0.5 gpl is achieved. The underflow mud is removed at
consistencies ranging between 400 – 600 gpl for further processing so as to
recover the entrained caustic and reduce the soluble soda of the mud to enable
safe disposal.
The settling is thus an important step in the Bayer process. To check the
suitability of flocculant and determine the exact dosages of the flocculant it is
necessary to conduct jar settling test in laboratory. The jar settling test is carried
out in a graduated cylinder of one litre capacity. The slurry after desired dilution is
flocculated by addition of flocculant and the rising of the clear interface with time
is noted and based on the sinking of the particles, the rate of settling is
determined. The overflow clarity is measured by carefully pipetting the liquor from
the clear zone and determining its mgpl solids. Further qualitative information on
compaction may be noted after a fixed interval of time. The height vs time plot
gives the settling rate. Normally the settling velocity is calculated based on the
time required for interface to travel from 800 ml to 600 ml i.e. in the clear zone.
4.1 Interpretation of the Settling Test Data for Estimation of Area
Requirement for Settling and Consolidation of Mud

Initially the height Vs time is plotted for the flocculated red mud slurry

Jar SettlingTest (Height vs Time)

450
Height, mm

350
250
150
50
0 5 10 15 20 25 30 35 40
Time, minutes

From the height vs time plot tangents are drawn to the curve. The intercept of the
tangent on the Y axis indicate the solids concentration of the mud at the interface
in the initial settling to these points.

Deriving values from Settling Curve

450
Height, mm

350
250
150
50
0 5 10 15 20 25 30 35 40
Time, minutes

Thus a plot of solids concentration vs time is obtained. Applying the Kynch

mathematical analysis the area required for settling can be calculated.
4.2 Factors Affecting Settling

4.2.1 Temperature

Higher temperature normally enhances settling rate. If the slurry is flocculated,

the higher temperature improves the flocculation and the frequency of interaction
of particles is higher.

4.2.2 Liquor Concentration

Too high liquor concentration reduces settling rate due to high viscosity of liquor.

4.2.3 Solids Concentration

The settling rate of the suspended particles depend on the solids concentration
and on the degree of agglomeration/flocculation as it determines the frequency of
particle interaction.

4.2.4 Settling Aid

Settling rate can be enhanced by promoting flocculation using settling aids. The
dosage of it depends upon the properties of the solid and electrolyte. There is an
optimum dosage for any flocculant depending upon the attainable floc size,
maximum settling rate and maximum underflow solids concentration.

4.2.5 Surface Area and Mud Height

Surface area of the mud particle is an important factor while settling. Similarly
settled mud height in the settler determines the degree of compaction. If the mud
height is kept more than there is a possibility that the mud in the unsettled form
may decrease overflow clarity.

4.3 Measurement of Settling Rate Using Radiometric Equipment

Use of radiometric methods for measurement of settling rate is based on the

principle that during settling only the solids concentration varies. The radiation
source mounted onto a common elevator will scan the whole height of the settling
tube. The detector on the other side measures the intensity of gamma rays. The
solids in the tube will absorb some of the gamma rays and the rate of absorption
depends on the local solids concentration. The measurements are carried out by
time programmed radiometric scanning of a substance (in suspension) filled in
the inner settling tube.
The inbuilt software based on the measurement of the intensity of radiation
calculates and gives: -
• Height (in cm) vs Solids concentration (kg/m3) at different time interval
• Velocity diagram i.e. velocity (in m/hr) vs solid concentration (kg/m3)
• Solid flux diagram i.e. solid flux (in kg/m2.hr) vs Solid concentration
(kg/m3)
 • Loading diagram i.e. Discharged solid concentration (kg/m3) vs Specific
solid loading (kg/m2.hr) to thickener

4.3.1 Solids Concentration Profile

Gives complete characteristics of the settling of the red mud with time as a
function of height. This reveals the rate of settling of various red mud particles in
the settler. It also gives information such as residue level height vs time. The
three profiles given below indicates the level of flocculation attain during settling.
These are under flocculated when the dosage of flocculant is inadequate, well
flocculated when the flocculant dosage is sufficient and over flocculated when the
dosage is higher.

4.3.2 Velocity Diagram

It gives solid content vs settling velocity graph on a semi logarithmic scale. With
this various parameters such as stokes velocity, average particle diameter etc.
can be calculated. Velocity diagram simulates the zone of actual settler (i.e. two
zone settling or three zone settling).
 Velocity Diagram

1
Velocity, m/hr

0.1
0.01
0.001
0.0001
140 210 280 350 420 560 700 840 980

Solids Content, gpl

4.3.3 Solid Flux Diagram

The solid flux diagram is derived from the concentration profile. The product of
the concentration and settling rate is termed as solid flux. The plot of solid flux vs
solid concentration gives the behavior of the settling.

Solid Flux Diagram

100
Solid Flux, kg/m² .hr

10

0.1
0 110 220 330 440 550
Solid Content, gpl
4.3.4 Loading Diagram

It gives the plot of the discharge solids concentration vs specific loading. This
data is useful in estimating allowable loading of solids in a continuous thickener.
This data may also be used for designing a new thickener.

Loading Diagram
Discharge Solids Concentration,

1200
1000
800
Kg/m³

600
400
200
0 10 20 30 40 50 60 70
Specific Loading, kg/m² .hr

4.3 Limitation of the Conventional Jar Test Method

•The temperature of the slurry cannot be maintained as that of the actual

settler
• The complete compaction of the underflow requires many hours which
cannot be studied by the conventional batch test
• To obtain rate of settling, specific loading solid concentration, underflow
compaction, and specific area requirement a series of experiments have to
be conducted along with tedious manual calculation
Though some of the data are calculated by kynch mathematical analysis, there
are some limitation to this empirical relations such as it assumes that particles
are of the same size and the velocity of fall depends only on the local particle
density.

4.4 Merits of SAM Over Conventional Jar Test Method

• The relationship between settling rate and underflow solids concentration,

specific loading of settlers, degree of compaction and specific area
requirement all can be obtained by a single laboratory test.
• The settling rate at each of the solids concentration found with sam are for
solids in the compaction zone, which are not possible by laboratory jar
tests.
 • Although, the simple jar tests are used to screen flocculant type and
approximate dosage, they very often mislead as to the thickenability of the
underflow, whereas, with sam this important aspect of the behavior
operating with the particular slurry and flocculant can be predicted.
• The condition of the settler can be very well maintained in this unit, i.e.
temperature.

4.6 Application of SAM

The traversing soft gamma ray absorption model (sam) can be used for the
following applications:
1. To select effective flocculant which may be starch, synthetic or
combination of both for each source of bauxite.
2. To optimise the dose of flocculant for proper thickening of mud.
3. To optimise the capacity of the thickener for full production rate of alumina.
4. To design thickener and deep thickener for future coming alumina plants
processing new source of bauxite.

5. Precipitation Processes

5.1 Introduction

The precipitation is basically the hydrolysis of sodium aluminate of the

pregnant/precipitation liquor with recovery of caustic soda according to the
following equation:

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

After bauxite digestion, the digested slurry is sent to the settlers where mud is
removed while the clear aluminate liquor is pumped to precipitation. The seeded
crystal growth technique is used for precipitation of the aluminate liquor, which is
achieved by chemical and physical effects. This process helps in producing
hydrated alumina along with its quality and granulometry. Liquor volume
recirculated per kilogram of alumina hydrate production is called as liquor
productivity. Improving precipitation process, optimizing liquor productivity and
hydrate quality is a subject of interest for alumina technologists world wide.

5.2 Mechanism of Precipitation

• Growth: Transfer of alumina from the solution to the growing particles

• Nucleation: Generation of new particles of very small size less than 1
micron. Rate of nucleation decrease with increase in temperature and may
be zero above 75°C
• Agglomeration: Combining or cementing of many fine particles into one
larger unit or agglomerate. It is favoured at high temperatures say above
70oC
 • Breakage and Arition: It is reverse of agglomeration. This includes gross
breakage of particles by direct impact with walls, impeller or other
particles.

5.3 Factors Affecting Precipitation

• Caustic concentration
• Molar ratio of the pregnant liquor
• Temperature profile
• Seed charge

a. Caustic Concentration

With the same molar ratio, a higher caustic concentration allows the
precipitation of more aluminium hydroxide per unit volume of liquor. A
higher caustic concentration at precipitation helps in achieving higher
digestion liquor conc. through the existing evaporation stage without any
additional energy consumption, which in turn offers the advantage of
increasing the alumina content in the digestion liquor. Molar ratio as low as
1.25 (0.77 A/C) can be obtained with 150 gpl Na2O while a molar ratio of
1.45 (0.66 A/C) can be obtained at 110 gpl Na2O concentration thus
enhancing the liquor productivity by nearly 35 gpl. Fig 1 shows the
characteristics of caustic concentration, MR with alumina precipitated.

Fig. 1 Effect of Na2O/Al2O3-MR and caustic concentration on

precipitated hydrate
Al2O3 precipitated per litre of

100
MR=1.25,Na2O=150gpl MR=1.35,Na2O=150gpl
90
pregnant liquor

MR=1.45,Na2O=150gpl
80
70 MR=1.35,Na2O=110gpl
60
MR=1.45,Na2O =110gpl
50
40
2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3

Ending MR

b. Molar Ratio of The Pregnant Liquor

The starting molar ratio (Na2O/Al2O3) determines the amount of aluminium

hydroxide, which can be precipitated per unit volume of liquor. So the
alumina charge at digestion stage is to be maximized to get lower molar
ratio resulting in higher supersaturation of precipitation liquor, which has
more tendency to precipitate with the reduction of temperature.
Fig.2 shows the value of molar ratio (A/C ratio) at which additional alumina
dissolved in digestion will yield extra alumina during precipitation.

Fig.2: Typical Precipitation Profiles Showing the Influence of the Starting A/C (or
MR) and the Productivity

0.8 100

Liquor productivity, gpl

0.75 MR=1.32
0.7 MR=1.38 80
0.65 PRODUCTIVITY
Liquor 1 60
0.6
A/C

0.55
40
0.5
0.45 Liquor 2 A/C 20
0.4
0.35 0
0 5 10 15 20 25 30 35
Residence Time (hours)

c. Temperature Profile Across Precipitation

The starting and ending temperature of precipitation process dictates the yield
and its granulometry. Higher temperature has higher equilibrium alumina
concentration resulting in decreased liquor productivity. Hence a plant
following a higher starting and higher ending temperature will have lower
liquor productivity. The temperature profile is selected based on the aim of
producing coarser (sandy)/ floury alumina. To maximize the yield and to
produce sandy alumina, it is essential to have a higher supersaturation, higher
starting temperature and a lower ending temperature. Lower end temperature
in precipitation results in a higher precipitation rate due to lower equilibrium
alumina concentration in the liquor. Hence a search of optimum temperature
profile is necessary for maximizing the yield for any given concentration and
molar ratio of the liquor.
In practice, the optimum profile can be approximated by optimisation of first
temperature and by introducing one or the several stages of intermittent
cooling. The temperature profile of 70– 50°C is considered ideal for the
operating alumina plants.

d. Seed Charge

The rate of crystallisation is proportional to the seed surface available for

crystallisation. Higher seed charge leads to higher surface area and hence
more liquor productivity. The excess seed charging will lead to generation
 of more fines in the circuit. In the plants not following seed filtration, the
seed charge can be increased upto 300 – 400 gpl and the plants following
seed filtration, the seed charge can be increased upto of 400 – 600 gpl .

Fig.3 shows the influence of seed charge vs liquor productivity.

Fig. 3 : Influence of the seed charge ,with and without seed

filtration ,on the liquor productivity

90
WITH SEED FILTRATION
Liquor productivity

85
WITHOUT SEED
80 FILTRATION

75

70

65

60
0 100 200 300 400 500 600
Solids in the end of precipitation slurry

5.4 Technologies Used

The two basic technologies prevalent for precipitation process are the European
and American technology. The European variant is characterized by higher
productivity operating at low temperature profile across precipitators, high seed
charge and results in the generation of floury alumina, while the American variant
uses low caustic conc., low seed charge and has low liquor productivity but has
the advantage of coarsened alumina.
The European process is operated closer to optimum conditions resulting in the
lower energy consumption due to higher liquor productivity. This type of
technology is at present being followed by BALCO refinery with the technology of
Aluterv – FKI, Hungary as shown in Fig.4.
 Fig. 4: European Process

Spent liquor

(filtrate)

Production
Precipitators
40 – 50
hours
Pregnant liquor

Seed Tank
One of the pecularities of the American process technology is the agglomeration
of fine seed particles at higher temperature. The important process stage in this
is the hydrate classification and the use of two different seed: fine and coarse
seed. This type of variant is being followed by HINDALCO refinery precipitation
process as shown in Fig.5.

Fig. 5: American Process

Pregnant
liquor

PT ST TT
Precipitator Spent liquor
overflow
25 –30 hours
Coarse Fine seed
Product hydrate for calcination
seed

Table-1 shows the comparison of the two processes

 Table-1: Comparison of the European and American process

Characteristics European American

Pregnant liquor: Na2Oc,gpl 145-150 105-110
MR 1.65-1.75 1.5-1.55
Seed solids conc.,gpl 200-400 50-120
Residence time, hours 50-70 30-40
Temp; °C – Starting 60 75
Ending 50-55 55-60
Liquor productivity, kg/m3 65-70 50-55
Product size (-45 µm), % 35-45, Intermediate 8-12, Sandy
Crystallisation mechanism Nucleation + Agglomeration +
adopted growth growth

The trend of conversion of floury to sandy alumina suiting to modern smelter

requirement is being practiced for material and energy saving measures. In this
context the productivity is also to be maintained intact and on the higher side. To
cope up with the recent requirement, the latest Alusuisse precipitation process
and Aluminium Pechiney high solid technology were developed having
advantage of higher liquor productivity and better granulometry of the product.
Alusuisse precipitation process or Alusuisse Hybrid technology is the hybrid of
the European and American variants achieving the high precipitation yield and
the required product quality together with granulometry. The temperature can
also be adjusted during the precipitation by means of appropriate selection of
interstage cooling to maintain a sufficient but not too high supersaturation. It is
also necessary to have control on agglomeration product by regulation of fine
seed. This process is divided into two phases. The salient features of the process
are detailed in Table-2.

Table-2: Salient Features of Alusuisse Hybrid Technology

Characteristics Phase-I (Agglomeration) Phase –II (Growth)

Na2Oc, gpl Upto 150 (fine seed) Upto 150 (coarse seed)
Seed in preg. liquor, gpl 50-120 200-400
Starting temp.,°C 70 <60
Residence time, hours 4-6 40
3
Productivity, kg/m 80
Grain size < 45 µm 5-10%

The most important aspect of the improved precipitation technology is the hydrate
classification and the use of different seeds. i.e. fine and coarse respectively. The
fine seed after filtration and washing can be subjected to agglomeration while the
coarse seed can be sent for growth directly.
Liquor productivity of 70- 80 gpl has been obtained in Gove alumina plant while in
Interalumina Venezuela more than 80 kg/m3 liquor productivity could be achieved
by using this technology. Fig.6 and Fig.7 detail the scheme of this type of
precipitation process.
 Fig. 6: The Alusuisse Precipitation Process

Cooling
Hydrate
Agglomeration IS Growth phase Classification

Product

Fine Coarse Seed

Seed Filtration Coarse seed
Fine Seed

Agglomeration Growth Phase

- Low seed charge - High seed charge
- High temperature - Low temperature

Fig. 7: Process Flow Diagram of Alusuisse Precipitation Process

PREGNANT LIQUOR Coarse Seed

Primary
classification
GROWTH
AGGLOMERATION PUMP OFF
PRECIPITATORS
PRECIPITATIORS
CALCINATION DELIQUORING PRODUCT HYDRATE
& WASHING

FINE SEED FILTRATION &

WASHING

SPENT LIQUOR
Thickener Secondary
classification

Pechiney technology has been introduced in new alumina plants. Indian alumina
plants use European, American and modified European (old version Pechiney)
technology. The modified European or Pechiney precipitation technology is
characterised by the high seed charge using the hydrate growth mechanism but
having the medium level liquor productivity (Fig.8). The HINDALCO plant
employs the American technology, the BALCO plant employs the conventional
European technology, and the NALCO plant adopts the modified European
technology.

Fig. 8: Pechiney Process with One Stage Classification

Pregnant liquor

15% < 45 µ
Liquor

Seed tank
58 0C

50 0C 14 % < 45 µ
75 kg productivity

Tbx
20 % < 45 µ

Production 7 % < 45 µ

Salient features of Aluminium Pechiney and Alusisse technology have been

compared in Table 3

Table-3: Comparison of The New Developed Processes: Aluminium

Pechiney & Alusuisse process
Characteristics Aluminium Alusuisse
Pechiney
Pregnant liquor:
Na2Oc,gpl 140-145 140-145
MR 1.65-1.70 1.45-1.60
Seed solids conc.,gpl 800 400
Residence time, hours 60-65 50-60
Temp;°C – Starting 60 75-80
Ending 55 50-55
Liquor productivity, 60-65 80-85
3
kg/m
Product size (-45 µm), % 8- 10 <5
Crystallisation Growth and Agglomeration, secondary
mechanism adopted secondary nucleation nucleation and growth
The Pechiney process being followed by NALCO Damanjodi refinery is
characterised by high caustic concentration as high as 145- 155 gpl and molar
ratio of 1.50 –1.55, high seed ratio of 3.0 - 3.5, low to medium temperature upto
initial 60oC with the limitation of low 2 -2.5 gpl organic content. The seed is
coarse 1 –12 % minus 45 micron and residence time of 45 hours. The most
significant mechanism is the crystal growth without agglomeration.
The hybrid technology consisting of American and European variants with high
utility of agglomeration has been successfully adapted in alumina refineries
abroad. The need of the hour is to optimize the precipitation process in Indian
alumina plants to get the maximum productivity and good alumina quality.

6. Future Alumina Quality

The experts of ALCAN and COMALCO have advised the long term alumina
quality specification expected on the “open market” with consideration of both the
metal market quality trends and reduction cell technology change in their Weipa
Feasibility study for a green field alumina plant. The forecast is reproduced in
Table 1.

Table.1: Future Alumina Quality Projections

Parameter Typical Range

Fe2O3, SiO2, % 0.012 max. 0.015
Na2O, % – short term 0.30 max. 0.35
- long term 0.25
Specific surface area, m2/g 70 60-80
Particle size, -45 microns, % 6 max.10
-20 microns, % <1 max.2
+150 microns, % 1 max. 5