AL Extr - H H
AL Extr - H H
AL Extr - H H
127
128 SYMPOSIUM ON NON-FERROUS METAL INDUSTRY IN INDIA
TABLE 1
1933 1939 1941 1943 1946 1947 1948 1949 1950 1951 1952
U.S.A. 39 149 280 835 375 518 565 603 718 836
Canada 16 75 194 450 160 269 320 369 397 445
Soviet Union 4 45 62 62 75 90 100 - - -
France 14 50 64 46 60 63 65 59 67 100
Italy 12 34 48 46 11 24 33 28 41 55
Norway 15 31 17 23 20 22 32 39 52 56
Great Britain 11 25 23 57 35 29 30 34 33 31
Switzerland 8 27 26 19 20 -- 19 23 21 29
Austria } 19 199 234 250 j- 8B 13 16 20 14
Germany ^- - 8 31 30 81
Japan - 23 65 133 3 2 10 23 28 37
Hungary - - - 9 2 - 9 9 - -
Sweden - 3 2 - 4 4 4 4 4 7
Total world 142 665 1220 1970 760 1070 1220 *1238 *1411 1691
production
All figures in 1000 tons. B: For W. Germany only. *Figures excluding Soviet Union.
on 10 July 1944 when the first aluminium Table 2 indicates the average production of
was tapped from the reduction furnaces of aluminium in India.
Messrs Aluminium Corporation of India Ltd.
at Jaykaynagar. The factory was opened
in 1937, but due to many unavoidable cir- Refining of Bauxite for the Manufacture
cumstances and troubles the production of Aluminium
could not be started before July 1944. The India has abundant deposits of bauxite,
Indian Aluminium Company, which started roughly estimated to be 250 million tons, of
working in March 1942 at Travancore State, all grades. The high-grade bauxite amounts
imported its alumina from Canada until 1947 to about 35 million tons distributed as
when they established their alumina plant under :
at Muri in Bihar.
The rise of production of aluminium of all M illion toils
the countries of the world is shown in Table 1. Madhya Pradesh 15.1
Orissa 8.58
Bihar 5.23
TABLE 2 3.23
Bombay
YEAR PRODUCTION Madras 2.00
(in tons)
Kashmir 1.00
1944 1729 Bhopal 0.25
1945 2254
1946 3237 Table 3 indicates the distribution of
1947 3218 bauxite of 55.0 and below 55.0 per cent
1948 3372
A1203 in different localities of these pro-
1949 3516
3590 vinces.
1950
1951 3876 Important analysis of the bauxite from the
1952 3566 different quarries and localities are given in
Table 4.
DUBE - EXTRACTION & REFINING OF ALUMINIUM 129
TABLE 3
HIGH GRADE LOW GRADE TOTAL
ABOVE 55% BELOW 55%
AI,O3 A1 ,O3
Madhya Pradesh
Baragawan Hill 1200000 2800000
Tikaria 2000000 5000000
Katni 1500000 ---
Tikuria 600000 -
Flag Staff Hill 1000000 3000000
Sirouj a 30000 3000000
Jashpur 150000 -
TOTAL 6480000 13800000 20280000
Bombay
Belgaum 75000 2000000
Nange and Kiniya 200000 ----
Radhanagri 2000000 -
Dhangarvadi 2000000 -
Thana 750000 -
TOTAL 5025000 2000000 7025000
Bihar and Orissa
Ranchi ( scattered ) 500000 110000
Dudha Pat 250000
Dudmatia Pat 500000
TOTAL 1250000 110000 1360000
Himalaya Region
Kashmir (Jammu) 1000000 1000000
TOTAL, all districts 13755000 15910000 29665000
Results of Bayer Extraction Tests of only coarse crushing of the ore and screening
Quartzitic Type of Bauxite out to -12 mesh fines :
TABLE 4
LOCALITIES A1 203, si o2, TiO, Fe2U3, L.O.I.,
% /0 %
Bihar
(a) Champi (Bagru Hill) 49.00 1.00 7.50 1700 24-50
(b) Tori 55-00 0.90 10.00 7-00 27-10
(c) Pakhar 5550 0.80 9.50 7-00 27.20
Katni 54-60 2.20 8.10 8.60 26-50
Madras Shevaroy Bauxite
(a) Salem 52-70 1-30 1-35 15-97 29.04
(b) Quartzitic type of bauxite 49.25 T.Si02 0-16 2-10 2526
23-10
R.SiO2
2.47
settle. The clear sodium aluminate liquor is for the manufacture of electrode are petro-
decanted and subjected to the process of leum coke and pitch. The petroleum coke
hydrolysis. The impurities are filtered should-be of highest purity containing only
through Kelly filter presses and the filtrate 0.2-0.3 per cent ash as the purity of the metal
containing the clear sodium aluminate liquor depends much on the purity of the paste.
is added to the process and the impurities The binding property of a pitch is responsible
are dumped outside. By the action of water for the manufacture of good paste. It has
under controlled temperature, concentration been noted that the binding property of
and quality and quantity of the seed and the Indian pitch is inferior as compared to the
stirring rate, the clear sodium aluminate pitch of other foreign countries. The in-
liquor is decomposed to . form aluminium ferior binding property results in dusting of
hydrate and caustic soda. The precipitated fine carbon and crumbling of anode pieces.
aluminium hydrate is filtered through Oliver Within the last few years many experiments
filter presses and calcined at 1300°C. in were performed to improve the binding pro-
rotary kilns to drive off the combined water perty of the pitch. It has been observed
and moisture. Alumina thus prepared is that the C2 value of the pitch plays an im-
fed in reduction furnaces for the manu- portant role for the binding property of the
facture of aluminium. Table 6 shows the pitch. But there is a great controversy
average analysis of red mud and alumina regarding the definition of C2 value. Accord-
produced from the bauxite of Bihar area- ing to Adam and Sach, C2 value is resinous
and it is usually defined as the resinous part
of free carbon soluble in pyridine, but accord-
TABLE 6
ing to Italian methods C2 value is the bitu-
R$n MUD ALUMINA minous carbon soluble in anthracene oil and
Loss on ignition , % 13-14
insoluble in benzene. These two methods
SiO„ % 3-4 0-06-0-070 give different readings. It has been found
Fe2O3 , % 24-25 0-03-0-040 that if the pyridine method gives 7.0 per cent
TiOa, % 27-28 0.02-0.025 C2 value, the Italian method gives about
Na2O, % 6-5-7.0 0-40-0-500
22.0 per cent C2 value of the same pitch.
A12Os, % 18-20 Remainder
The higher the C2 value, better is the binding
property. C. value of a good pitch by the
For the manufacture of 1 ton of alumina Italian method should be of the order of
the requirements are approximately as 24-25 per cent. Table 7 indicates the ana-
follows : lysis of pitch from various sources.
Bauxite 2.2-2.4 tons For the manufacture of paste, the raw
Caustic soda 0.08-0.11 ton petroleum coke is calcined in Reidhammer
Steam 8-10 tons furnace, crushed and ground to find out the
Fuel oil 0-18-0.20 ton granular composition where the litre-weight
is the highest. It is mixed with 25-28 per
Electrodes cent of the pitch and sent to the reduction
furnaces. The heat of the furnace drives
Pre-baked electrodes and Soderberg conti- away the volatile matter of the pitch and it
nuous type electrodes are the two main types forms a solid mass.
of electrodes used in reduction furnaces.
Advantages and disadvantages of these elec-
Reduction
trodes will be discussed later on. Soderberg
continuous type of electrodes are used in Electrolysis - The theory of electrolysis is
both the plants in India. The raw materials not yet fully developed. Many theories are
^. l,.la „ . ^ ..l l.,i..a. ^.I.ibLLIL LiL_I 1._,•.' NWW. '"^tll ,___ U. JL
TABLE 7
TOTAL C, C, COKING ASH, SOFTENING
FREN VALUE , VALUE, VALUE , % POINT,
CARBON, % % % oC.
put forward and they are very interesting to About 80-90 per cent of Na reacts with
study. The simplest theory which is re- AIF3 and a small portion vaporizes and meets
garded as the basis of practical work still CO2 at the anode to form Na20 and CO.
holds good. The alumina gets dissolved in Current Efficiency -The electrolysis of
molten cryolite at 950°C. and it gets decom- the molten substance differs to a great extent
posed by the electric current. with that of aqueous solutions. Most of the
2A1203 - 60 + 4A1 aqueous electrolytes give nearabout 100
60 + 3C -^ 3CO2 per cent current efficiency, but in the electro-
60 + 6C -- 6CO lysis of aluminium the efficiency is only 80-
85 per cent. There are many reasons for
Oxygen is the primary product and the the low current efficiency:
quantity of CO2 and CO formed as the result (1) Losses by Va' orizat' 'on- This is sup-
of the combination of carbon with oxygen ported by Gadeau's theory and he considers
depends on temperature and certain other this as the most important factor for the
conditions. Assuming that alumina is the low current efficiency.
solvent, the following theory has gained (2) Loss by Me Formation of Metal Fog -
popularity. It indicates that alumina is the The formation of the metal fog much depends
solvent and sodium fluoride, one of the com- on the temperature of the furnace. The
ponents of cryolite, undergoes electrolytic higher the temperature, the more the cathodic
decomposition. The reactions are as under: oxidation and formation of metallic fog.
12NaF -} 12Na + 12F It has been observed that even a slight rise
12Na + 4A1F3 --k 12NaF + 4A1 of temperature above the maximum causes
12F + 2A1203 - 4AIF3 + 60 the current efficiency to fall to a great extent.
and so final results again come to Our records indicate that the temperature of
the furnace is generally between 950° and
2A1203 ---) 4A1 + 60
1000°C. The temperature of 1000°C. is
This theory tells that cryolite is continually too high as it takes a lot of current for no
decomposed and formed. good use. The rate of reoxidation also
Another interesting theory is developed depends on the distance of anode and cathode.
by Gadeau. His theory indicates that For a 12,000-13,000 amp. furnace the dis-
Na2O, which is always present in the molten tance may be as small as 3 cm., but furnaces
bath, is responsible for the main reactions: of self-baking electrodes of larger dimensions
6Na20 -- 12Na + 60 require a distance of 6-7 cm. Adjusting of
12Na + 4AIFa - 12NaF+ 4A1 this distance is one of the important opera-
60 + 3C --> 3CO2 tional problems. If the current distribution
12NaF + 2A1203 --^ 4A1F3 + 6Na20 is uneven, it results in overheating or cooling
DUBE - EXTRACTION & REFINING OF ALUMINIUM 133
of certain portion of the bath and it also (b) reduced electrochemical effect of the
accelerates the reoxidation. reaction of oxygen with carbon to
(3) Due to the dusting of anode the carbon form C02; and
floats on the molten bath and thus a portion (c) some reversible reactions between
of current passes through these fine particles cathode and anode which are not pro-
of carbon and not through the bath. This perly studied.
partial short circuit of the cell occurs The decomposition voltage of a self-
either between the electrodes and the metal baking large electrode comes to nearabout
or between the electrodes and the sides of 1.55-1.6.
the cell. If the dusting is excessive, it is Type of Electrodes - Throughout the
detrimental for operation of the furnaces. world the multiple-pre-baked electrodes and
(4) The density of molten aluminium the self-baking Soderberg type of electrodes
(2.3) is slightly more than the molten bath are used in the reduction furnaces. It is
(2.2) and so aluminium is not properly sepa- very difficult to say which type is more ad-
rated from the bath and it has a temperature vantageous, but Soderberg type of electrodes
about 300°C, above its melting point. are gaining prominence. It is very difficult
Decomposition Voltage - It is necessary to to enclose a furnace using multiple-pre-baked
have the knowledge of the decomposition electrodes and to make arrangements for the
voltage while operating a particular type of recovery of fluorine , and the periodic with-
furnace . It guides in the results of heat drawal of the electrodes and the introduction
balances and other factors. Many data have of new electrodes results in discontinuity of
been found out by different electrochemists cell operation. Otherwise the multiple-pre-
and they differ from 1-75 to 1.5. The theore- baked electrodes are simple and give satis-
tical decomposition voltage is nearabout factory operating results ( FIG. 2) _ The self-
1.15 volts. The difference between the baking electrode can be enclosed in a box-
theoretical- and practical decomposition like frame and the fluorine and other tar
voltages may be attributed to the following: matters, etc., can be removed easily and can
(a) A12O3 is not completely saturated in be separated in an adjoining fluorine-recovery
cryolite; plant. Soderberg continuous type of elec-
FIG. 2 - CROSS - SECTION AND DETAILS OF INSTALLATION OF A 30,000 AMP . MULTIPLE - PRE-BAKED CELL
134 SYMPOSIUM ON NON-FERROUS METAL INDUSTRY IN INDIA
trode forms one compact mass and has lower The mesh size of alumina to be used in the
current density than multiple-pre-baked elec- reduction furnaces is a matter of controversy.
trodes. Some operators prefer coarser alumina and
some finer. Coarser alumina generally comes
under 40-50 per cent -200 mesh and below
Effect of Impurities Present in Raw
this it is generally termed as finer alumina.
Materials
Our experience shows that finer alumina
The main raw material is alumina. The has a tendency to sink at the bottom of the
purity of this should be thoroughly checked. furnace and thus make the cathode dirty.
Generally the Bayer's process alumina is
quite suitable and the impurities like iron, Operation
silicon, etc., have not much effect on electro-
The molten cryolite dissolves theoretically
lysis, but even a little amount of vanadium
20-0 per cent alumina, but in practice it is
and phosphorus present in alumina may lead
not more than 8-10 per cent. The average
to a trouble in operation as it increases the
voltage of the cell is at 5.0-5.5 volts. When
resistance of th° cell. Current efficiency is
the concentration of alumina in the bath falls
lowered and the furnace runs hot. The
to 1.5-2-0 per cent, the voltage jumps to 40-
Indian bauxite contains both these impurities
50 volts. This phenomenon is called ` anode
and when the bauxite is digested with caustic
effect ' and it indicates that fresh addition of
soda these impurities find their way together
alumina is required in the furnace. An
with the alumina in the solution. The
electric lamp is connected in parallel to the
alumina produced gets contaminated with
cell which lights up during the anode effect
these impurities, and so it is always advisable
and attracts the attention of the operator.
to remove these impurities while refining the
This should not be allowed for more than
bauxite for the manufacture of alumina.
2-3 min. as during anode effect the tempera-
Titanium, to the extent of 0.04-0.05 per
ture of the furnace increases considerably and
cent, is not harmful in electrolysis, but if the
lot of cryolite and paste are lost for nothing.
metal is used for the manufacture of electric
It seems that during the anode effect the
cables, even 0.01 per cent of Ti lowers the
voltage increases due to the formation of a
conductivity of the product. Proper care
very thin layer of anodic gas which surrounds
is necessary for the prevention of TiO2 to be
the anode when the alumina concentration
precipitated along with aluminium hydrate.
falls to a certain value. The molten bath
The influence of Ti and vanadium on con-
does not wet the anode and the electric
ductivity is shown in Table 8.
current passes from the anode to the bath
through small electric arcs and thus over-
heats the bath. The recent practice is to
TABLE 8
prolong the period between two anode effects.
SILICON IRON TITANIUM VANADIUM SPECIFIC Generally an anode effect occurs between
RESIS-
TIVITY,
3 and 4 hr. The practice which does not
M I CROH M allow the anode effect to appear is called
AT 20'C.
` scheduled stirring'. The quantity of alu-
0.15 0-35 0010 0-012 2.85 mina is calculated in a way that after regular
0.14 0.26 0.020 0.010 2.87 interval the calculated alumina is added to
0.14 0.24 0.040 0.013 2.94
the bath and thus avoid the anode effect.
0.19 0.19 0-005 0-014 2-81
0-22 0 .22 0-005 0028 2.90 This is a very delicate process and a very
0-21 0.18 0.005 0.049 3.07 correct calculation is required. If the quan-
tity of alumina is more than the calculated
DUBE - EXTRACTION & REFINING OF ALUMINIUM 135
quantity, the alumina gets deposited over the open type furnaces. The invention relates
carbon cathode and makes the cell hot. The to continuous self-baking electrode type.
advantages of this practice are that unneces- It is based on the fact that the whole of the
sary loss of cryolite, electrode and current is furnace gas develops in direct contact with
saved. The approximate consumption of raw the electrode, and bubbles up through the
materials and power for the manufacture melt close to the surface of electrode dipping
of 1 ton of aluminium are shown as under: into. The lower end of the electrode is sur-
rounded at the bath surface by a small gas
Alumina 1 . 95-2.0 tons
chamber. The arrangement can be safely used
Cryolite ' 0.09-0.1 ton
Aluminium fluoride in Soderberg electrodes with vertical studs
0-015 - 0-02 ton
inserted in the chamber from the above and
Paste 0.6-0.62 ton
Calcium fluoride the current is supplied through them. The gas
0-01-0 . 015 ton
chamber outlets are connected into a pipe
Power 23,000-24,000 kWh.
which carries the gas to the washing plant.
At the Aluminium Corporation of India
Ltd., 24,000 amp. furnaces are operated.
Refining of Aluminium Metal
The power is supplied to the furnaces from
the Company's own thermal station. If precautions are taken to use alumina,
Improvements are being done in the paste and cryolite of high purity, it is possible
design and working of the furnaces. In to manufacture aluminium metal of 99-6-
modern plants the tendency is to go for 99.7 per cent purity . The main impurities
40,000-50,000 amp. furnaces. The furnaces are iron and silicon and other impurities like
are of enclosed type so as to facilitate the copper, titanium , vanadium, manganese,
recovery of gases and tar products ( FIG. 3 ). magnesium and sodium also find their way
But the enclosed type of furnaces, however, in traces in aluminium metal . For many
involve comparatively large and expensive purposes covering a large field due to its
installations and the operation of the furnaces better tensile strength than super-purity
behind the closed doors becomes more diffi- aluminium ( 99.99 per cent ) and tolerable
cult to inspect and control. Messrs Dett resistance to corrosion , the commercially
Norske Aktieselskab for Elektrokemisk In- pure metal is quite satisfactory . But at the
dustry, Norway, have patented a new furnace same time metal of super- purity has its own
in which they have provided an arrangement advantages and has extremely valuable
containing the advantages of enclosed and properties like high resistance to corrosion
I I
- - --------------
0
FIG. 3 - ENCLOSED 25,000 AMSP. FURNACE
^J +i L I I^, t ! '..L l .. ^wuu^xWl'r': - LLJ i r k
But if iron and magnesium content is very trialization and defence of the country. It
high, the scrap metal is subjected to the pro- is expected that the Government would take
cesses of preheating first in a resistance fur- keen interest and extend facilities and help
nace to eliminate the heavy metals and then for the progress of the aluminium industry.
in an arc-type furnace using NaCl, KC1 and
cryolite and carbon electrodes to eliminate Acknowledgement
magnesium and then subjected to final The writer wishes to acknowledge the
refining. suggestions made in writing this paper by
Fig. 5 shows the flow sheet of a full scrap- Mr. S_ C. Jain, General Manager of the
refinement plant at Ranshofen Plant, Ger- Aluminium Corporation of India Ltd., and
many. is grateful to the management of Aluminium
Corporation of India Ltd. for allowing to
Prospects of the Industry in India publish some of the plant data.