Physico Chemical Aspects Of Alumino-Thermic Reduction

In The Production Of Low Carbon Ferro-Alloys

by
D. D. Akerkar
Deputy Director (Retired)
National Metallurgical Laboratory
Jamshedpur 831 007.
Introduction
No doubt Carbon is the oldest, most extensively used and cheapest reducing
agent for the extraction of metals, and ferro-alloys, but due to its high affinity for
many metals it results in the formation of undersirable carbides. The growing demand
of carbon free alloys has generated considerable interest in aluminothermic reduction
of various .oxides. A common example of aluminothermic reduction is the thermit
welding of rails and repair of steel castings. As early as in 1898, Goldschmidt (1)
demonstrated the use of aluminium as a reducing agent in the production of refractory
metals. Subscquently, aluminothermic reduction has been extensively used to pro-
duce pure metals such as chromium, manganese and master alloys such as carbon free
chromium-aluminium, titanium - aluminium, ferro-chrome, ferro-molybdenum, ferro-
columbium, ferro-tungsten and ferro-titanium of high purity. Aluminothermic tech-
niques have led to notable developments in the field of high purity special steels. The
objective of aluminothermic reduction is to utilise the exothermic heat of the reaction
for smelting purposes. Aluminothermic reduction did not generate much interest till
1950's due to various reasons such as high cost of pure aluminium and lack of
available means for the removal of residual elements and oxides. The interest in
alumino-thermic reduction , revived in 1960's and onwards. Since then extensive
research work has been, carried out on aluminothermic reduction for producing low
carbon ferro-alloys by obtaining 95-96% pure metals from their pure oxides and also
metallic values from their oxides available as secondary sources.
The various factors that are to be considered in aluminothermic reduction are
density, melting 'point solubility, vapour pressure and viscosity of thereactants and
products. Kinetic considerations are relatively less important as the aluminothermic
reductions are quite rapid mainly due to the high temperatures involved due to
exothermic liberation of heat and the conditions are close to equilibrium. Develop-
ment of aluminothermic techniques for ferro-alloy production is important under
Indian conditions and various low carbon ferro-alloys have been produced by
aluminothermic reduction of oxides of respective alloying element along with iron
oxide/iron scrap at National Metallurgical Laboratory, Jamshedpur. Aluminothermic
reduction technology have been economically trasferred to. industry, and most of the
low carbon ferro-alloys produced in the country in eighties used to come from the
NML technology.
7.01
During aluminothermic reduction, the ferro-alloys are produced from their
oxide ores by reduction with aluminium using the exothermic heat of the reaction.
Temperatures of reaction may rise to anywhere between 1800 and 2500C depending
on the exothermicity' of the reaction and specific heat of the products. The reduction
reaction can be represented as :
Metal Oxide + Al ---> Metal + A1203
If the aluminothermic reactions are extremely fast and heat of reaction is
excessive so as to give higher temperature than required, some coolant such as iron
scrap or fillings or other inert materials such as lime or crushed slag are added to the
charge. It reactions are sluggish and enough heat is not generated during the reaction
to give liquid products, the reactants may be preheated to 200-600C. Sometimes an
energiser or booster such as barium peroxide, potassium chlorate, Cr03 or oxygen rich
salt such as NaNO3 etc., are added to increase the heat of reaction. Generally the
aluminothermic reduction reaction is spontaneous and the entire reaction gets com-
pleted within a few ntiniutes. It is estimated that for the process to be self sufficient
in its heat requirements and good separation of metal and slag, the specific heat effect
of the process should be 650-750 K calories per Kgm of reacting substances.
Experimental
Reaction Vessel : Fig. 1 shows the detailed drawing of a reaction vessel and Fig.
2 that of a former for the purpose of monolithic lining of the reaction vessel. The
reaction vessel is usually 'made out of mild steel of 3 mm thickness sheet. The size
of the reaction vessel depends upon the capacity of the plant. Usually three fourth
of the vessel's volume is utilised for reaction purposes. The lining thickness of
the reaction vessel is usually 100 mm. A semi-permanent lining of magnesite bricks
of one course is lined by suitable cutting of bricks, on the surface of which a rammed
lining is made with dead burnt magnesite powder of -70 mesh bonded with 3 percent
sodium silicate. After ramming, the vessel is kept for drying, the former is removed
and the vessel is allowed to dry, slowly preferably for a. day. It is then fired under
oil burner and pre-heated. It is of utmost importance that the lining is thoroughly
dried as the presence of moisture may create a lot of problems namely the leak out
of the metal and slag and even explosion. The higher the degree of preheat, the better
will be the results of a reaction.
Preparation of Charge Mixture : The charge mixture consists of ore which must be
of uniform size and well dried to drive away the absorbed and combined water. Also
any carbonates, if present, should be decomposed. The overheated materials should
be cooled to a temperature lower than the fusion point of aluminium (650)in order
to prevent the boiling up the charge before the final mix. After preheating, the
charges is mixed with aluminium powder and fluxes in a blender or mixer suitably
designed for thorough mixing. In the case of smaller reactions, this can be done by
hand on a suitable clean plateform. Only at the end of mixing, the energizer is mixed
with the charge. The prepared charge is then fed into the reaction vessel either by
7.02
of preheat, the better will be the results of a reaction.
Preparation of Charge Mixture : The charge mixture consists of ore which must be
of uniform size and well dried to drive away the absorbed and combined water. Also
any carbonates, if present, should be decomposed. The overheated materials should
be cooled to a temperature lower than the fusion point of aluminium (650)in order
to prevent the boiling up the charge before the final mix. After preheating, the
charges is mixed with aluminium powder and fluxes in a blender or mixer suitably
designed for thorough mixing. In the case of smaller reactions, this can be done by
hand on a suitable clean plateform. Only at the end of mixing, the energizer is mixed
with the charge. The prepared charge is then fed into the reaction vessel either by
hand or by simple chutes operated manually.
Process for the Production of Low Carbon' Ferro-Alloys : Firstly, a small 'quantity
of the charge mix is placed at the bottom of the preheated vessel and the ignition
mixture in a paper packet is placed centrally over it and ignited. When the ignition
starts, the charge is slowly fed in on the top of it. Care is taken to ensure that it is
uniformly spread over the entire area 'of the reaction vessel and the mixture is fed at
a rate that the melt surface is covered with a thin layer of it. If the rate of charging
is slow, it will expose the melt surface to the atmosphere and consequently increase
the heat losses. Excessivelyrate of charging will slow done the reaction and may
result in poor recovery. The advantage of bottom priming method is that the charging.
can be continued until the reaction vessel is full thereby utilizing the full capacity of
the vessel.
After completion of the reaction, the metal is allowed to solidify and cool.
When cooled, the solidified mass of slag and metal is separated from the vessel.
Further, metal is separated from slag by simple knocking with an hammer. Likewise
various low carbon ferro-alloys such as ferro-manganese, ferro-chrome, ferro-
vanadium ferro-titanium, ferro-boron, ferro-silico zirco-nium and ferro-tungsten, con-
taining trace to 0.1% carbon can be produced. The compositions for these low carbon
ferro-alloys are mentioned in Table I and Figure 3 illustrates various steps of their
production.
Thermodynamics : Auminiuum is the best commerical reductant because A1203 is
much more stable than most metal oxides. The aluminothermic reduction reaction
can be represented as :
3M0 + 2A1 = A1203 + 3M
(1)
The Gibbs energy change associated with the reaction provides the driving force
for the aluminothermic reduction process. Figure 4 represents the Gibbs energry
changes involved in the reduction of various oxides by aluminium. It is obvious from
Fig. 4 that most oxides, except Z102 and Ti02, can be readily reduced by aluminium.
7.03
The equilibrium constant for reaction (1) is given by :
K = [a
(A1203) M
A2
L-3MO - AP
The equilibrium constant K is a function of temperature and is constant at given
temperature. The factors promoting the aluminothermic reduction reaction are :
i) Lower activities of A1203. This can be done by adding fluxes such as CaO
ii) Lower activities of M. This can be achieved by alloying.
iii) A lower temperature which promotes the reduction reaction since most
aluminothermic reduction reactions are highly exothermic.
This enthalpy change is necessary to calculate the thermal balance of the
reaction and to predict whether the heat generated will be sufficient to melt the metal
and the slag and to separate them into two layers without the use of a furance. The
amount of heat released per unit mass of reactants can be calculated as follows :
AH
298
= AHA1203 - AEI
MO
.. (4)
Tabel II shows 4, 5 and 6 heat of reaction, calories per Kg of reactants, for
various reactions producing low carbon ferro-alloys. The heat of reactions involving
these boosters are also presented in figure - Preheating of the charge to a temperature
of 500
C has also been found to give encouraging results in alumino-thermic
reduction. Aluminothermic reduction reactions which produce excess heat may be
violent and they may be controlled by adding thermally inert materials e.g., lime is
used in some aluminothermic reactions. These inert materials are also called as "heat
sinks".
From the above a generalised statement may be made as follows :
For a controlled reaction to take place, between 600 to 1100 Kcal/kg of total
charge are required. Above 1100 Kcal, the reaction is violent and below 600 Kcal
it is very slow and booster or energizer may be added or preheating of the charge may
be necessary.
Melting Point : In an aluminothermic reduction, the melting point of the metal and
slag produced should be such that both of them are clearmelted during the proces.
The refractory metals like molybednum, tungsten, vanadium etc., may present
difficulties during melting. When the ferro-alloys of these metals are to be produced,
the melting points are usually lowered and the problem of melting is less severe. The
alumino-thermic reactions may present some difficulty during ferro-alloy production
when the thermal load is high. The melting point of metallic oxides may be lowered
by suitable flux additions. In this connnection lime has been found to be the most
effective flux as small amount of lime helps to decrease the melting point of alumina
7.04
considerably. Lime addition, besides lowering the melting 'point of slags, also
reduces the overall reaction temperature, as a part of heat generated in the procss is
consumed in fusing CaO. Therefore, only the optimum amounts of CaO should be
employed so as to conserve the heat balance of the reaction and also minimize the
losses of metal oxides in some cases.
Density : The density of the liquid slag and the liquid metal play significant role in
the separation of two phases after the ,completion of the aluminothermic reaction.
Larger the difference 'between the densities of liquid slag and liquid metal, better the
separation of two phases. Generally most of the liquid slags have a low density of
around 3 gm/cm' while most of the liquid metals have much higher densities.
Therefore the separation of the two phases does not usually present any difficulty.
Slag metal separation depends upon aluminium to metal ratios also. Higher A/M
ratios although decrease the melting point of metallic phases but result in poor
separation due to decrease in the densities of metallic phases.
Solubility and Chemical Affinity : The solubility and chemical affinity of the metals
and compounds involved in aluminothermic reduction with other metals and com-
pounds affect the reduction reaction significantly. The chemical affinity between the
reductant and the reduced metal may decrease the thermodynamic activity of the
reduced metal in such a way as to provide extra driving force for the aluminothermic
reaction to proceed in the forward direction. Also when the reductant and the reduced
metals have high mutual solubility or chemical affinity, the production of pure
reduced metal will not be possible as it will be contaminated by the reductant. This
happens in the aluminothermic reduction of titanium dioxide, TiO2 by aluminium.
Sometimes the reaction between the compound to be reduced and the compound
formed in aluminothermic reaction affects the reaction in an adverse . way e.g.,
aluminothermic reduction of chromic oxide, Cr203 is the case where interaction
between alumina and chromium oxide limits the progress of the reaction, and a high
metal recovery becomes difficult. On the otherhand, the presence of a compound
which reacts with product compound in aluminothermic reaction facilitates the
reaction in the forward direction by decreasing the activity of the product compound.
Thus lime can be used in alumino-thermic reactions to decrease the activity of
alumina.
Vapour Pressure and Viscosity : The vapour pressure of the metal and slag phases
at the reaction temperatUre significantly influences the separation between the two.
Lower the viscosities of metal and slag phases, better is the sep. ration. Generally the
viscosities of metals and alloys are much lower than those of liquid slags.
Therefore the viscosity of the slags is to be considered seriously. Usually the slags
produced during aluminothermic reduction processes are highly viscous and their
viscosity can be considerably decreased by suitable flux additions. Lime and
fluorspar have been suitably used as fluxes in order to reduce the viscosity of such
slags.
7.05
References :
1. Thennit Welding by Hans, D. Fricke, Metals handbook, 9th edition, 1983, Vol.
6, p.692.
2. Symposium on ferro-alloy industry in India, Organized by the National Metallur-
gical Laboratory, Jamshedpur, 1962, p.174-186.
3. Richardson & J.H.E. Jeffes, Journal of Iron and Steel Institute, 160, 1948,
4. Ibid 163, 1949.
5. Ibid 171, 1952
6. 0. Kubaschewski & C.B. Alcock, Metallurgical Thermochemistry, 5th edition,
Vol. 24, 1979.
7.06
Ti - 35-40 Min.
Si - 3% Max
C 0.1% Max
Al - 20% Max
S - mo Max
P - 0.1% Mai.
Ti - 40.6%
Si - 3.1%
C - 0.07%
Al - 11.1%
S - 0.04A
P - 0 . 0 8
FERRO-MOLYBDENUM
Mo 60-70% Min Mo - 70.02%
Al - 0.5% Max. Al - 0.10%
Si - 2% Max. Si - 0.23%
TABLII-1 ; ANALYSIS OF VAAJOUS LOW GAIWON Fki;RAO-ALLOYS
INDIAN
S.
EilIgalkALMIL

1111)114.4P. EligaaA4ALAU
FSRRO-CHROME

FERRO-MANGANESE
Cr - 65-75% Cr - 69.58%
Si - 1.5 max Si - 1.57
C - 0.09 Max C 0.03
S - 0.05 " 3 -0.03%
P - 0.03 " P_ - 0.004%
Mn - 80-85%
C 0.06% max
S - 0,05% Max
P 0.06% Max
Si - 1.0% max
Mn - 81%
C - 0.04%
- 0,04%
P
0.05%
Si - 8%
FERRO-VANADIUM

FERRO-TITANIUM
V - 50% Min. V - 52.37%
Si - 1.250ax.Si- 14%
C 0.23 " C - 0.06 %
S - .1% 0.06%
P - 0
Q
.1% " P r Q .07%
Al - 1.5% " Al- 1.14%
FRRRO-SILICO-ZIACONIUM
Zr ,a5.40 Min Zr - 354.68%
Si - 47-52% Max Si - 15,93%
C - 0.3% Max C - 0.46%
FRHAO-TUNGSTEN
W - 70% Min W - 76.86%
Si- 1% !Max Si- 0.97%
C - 1% Max C - 0.08 %
Mn- 0.8% Max Mn- 0.34%
Al- 0.3% Max. Al- 0.4
3 - 0.06% Max. 3 - 0.02%
P , 0.06% Max. P r 0.04%
FLaRO-BORON
B - 17% Min
Si - 1.5% Max
C 0.5% Max.
Al - 0.5% Max.
B
Si - 0.95
C 0.35%
Al - 0.55%
7.07
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