was reported that 94% of iron was separated from red mud at
AbstractConventionally metallothermic reduction processes 1600 C and a slag containing titania, alumina and silica.
are used in metallurgical application for production of metal or Chlorination of red mud was suggested for partial separation
carbides. Theses processes are highly exothermic reactions of iron oxide as a iron chloride[19]. Mixture of red mud,
occurring between a metal oxide and reducing metals. In this carbon was calcinated at 900 C and then was chlorinated at
study, an aluminothermic reduction process was presented for
500 C to produce iron chloride.
the production of ferro alloy composites. Seydiehir red mud
sample was used as a metal oxide source which contains
Beside of pyrometallurgical processes, there are a number of
considerable amounts of reducible oxides such as silica, iron and investigations on the recovery of valuable oxides by
titanium oxides. With the addition of solid carbon and powder hydrometallurgical applications. Although pyrometallurgical
aluminium to the Seydiehir red mud a homogeneous mixture processes require high temperature and high energy costs,
was formed after ball milling for 6 hours. The mixture in liquid hydrometallurgical operations are more feasible and less
metal phase was reduced by heating at a temperature of 1000 C costly. One of the valuable oxides in the red mud is titanium
under carbon monoxide gas. The results obtained from thermo dioxide. For recovery of it, H2SO4 and HCl acid leaching
gravimetric (TG)/differential thermo gravimetric analysis processes were investigated[11, 12]. It was reported that, 64%
(DTA), X-ray diffraction (XRD) and energy dispersive analytical of titanium dioxide was recovered by sulphur acid
X-ray (EDAX) analyses were used for interpreting the reactions
and the processes. The effect of several variables such as time,
leaching[11]. In another investigation, a higher percentage on
temperature, aluminium and carbon content on the effectiveness the recovery of titanium dioxide was reported by the same
of the process was evaluated by identifying the reaction products acid at 90 C[12].
which were rich in iron and iron aluminium silicon compounds. The fundamental industrial processes used for extraction of
single oxides such as iron from red mud demonstrated to be
KeywordsAluminothermic, reaction, red mud, ferro alloy economically unsustainable. The iron oxide content of the red
mud can not be considered as competitive raw material for
steel making because of it is lower than commercial iron ore.
I. INTRODUCTION This kind of single oxide application generates new solid
waste again. Therefore, development of a novel economic
he metallurgical processes employed in primary industries process to recover valuables from red mud while minimising
213
A. Atasoy
sample was provided from the Seydiehir alumina plant at total is the ferric oxides that are reducible while the remaining
Seydiehir in Turkey. Solid carbon was provided from 37% is non reducible part or can be called as refractory
Turkish Petroleum Refineries (TUPRAS) at Izmit in Turkey oxides.
and metallic powder of aluminium (purity of 99% and 300
mesh size) was also used. Aluminium and carbon powders Table 1: The chemical composition of the sample used from
were added in stoichiometric amounts for the reducible the Seydisehir plant
oxides. The starting mixture was homogenized by
Oxi Fe2O3 Al2O3 SiO2 TiO2 Na2O CaO LOI Othr
conventional ball milling for 6 hours.
Wt. 42 24 15 6 10 1.5 1.5
%
214
Reduction of Ferric Oxides In The Red Mud by The Aluminothermic Process
assumption can be made based on the weight loss of 2 FeO(OH)(s) Fe2O3 (s) + H2O(g) (1)
physical/crystal water, oxygen content of the oxides in the Al (s) Al (l) (2)
sample. On this assumption, the TG curve can be divided into
nine regions. Up to the melting point of the metallic As seen from the curve, the peaks are in different size and
aluminium powder, any reactions between oxides and shapes. The second exothermic peak is at around 960 C, the
reducing materials were not expected. Up to 600C, the third one is at 1050 C. The peaks indicate that there are
observed weight loss is around 6% which could be related to several exothermic/endothermic and transformation reactions
the dehydroxylation of FeO(OH) and AlO(OH) phases and the in the mixture during the aluminothermic reduction process.
volatile content of the red mud. At higher temperatures, up to As explained above, the used red mud sample contains
780C, the observed weight loss could be related to the different oxides. It calls as a complex mixture. The exothermic
decomposition of sodalite group phases attributed to the CO2 peaks were assumed to be the reduction of ferric oxides
evolution due to the red mud in the mixture. It is suggested content of the red mud. Processing of complex concentrate,
that, the weight loss between 780-1100C is related to the such as chromite, was well illustrated, that the reduction takes
removal of any gases as a result of the reduction reactions place step by step according to stability of oxides in starting
between oxides and the reducing materials. All possible material[26, 27]. A common observation of these oxides, in
reactions take place in the regions of 7-9 above 780C. The the first step, FeO is reduced and Fe2O3 is reduced to metallic
total weight loss above this temperature is 12.1%. The results form. Later on, titanium oxide and silica are reduced to
indicate that there are formations of metallic and gaseous metallic state. The reduction mechanism of the ferric oxides
products. Any weight gain could be related to the formation of were presented in the below. The reduction of hematite
alumina by the reaction between metallic aluminium and content of the red mud by aluminothermic process, the
oxygen, but the experiments were carried out under nitrogen following reaction can be given as a summary;
atmosphere and as seen from the TG curve, there was no
weight gain in the sample. The summary of the Fe2O3 s (in red mud)+ Al s 2Fe s + Al2O3(s) (3)
thermogravimectric analysis of the mixture of red mud, carbon
and metallic aluminium powders was presented in Table 2. However, the reduction of hematite takes place steps by steps
with the following reactions;
Table 2: Summary of the thermal behaviour of the mixture.
3Fe2O3 s (in red mud)+ 2Al s 6Fe3O4 s + Al2O3 s (4)
Steps Temp. gap Weight Explanation
lost
Fe3O4 s (in red mud)+ 2Al s 3FeO s + Al2O3 s (5)
1. 25-120C 0.5% Evaporation of physical water
2. 120-250C 2.5% content,
3. 250-270C 1.2% Decomposition of gibbsite 3FeO s (in red mud)+ 2Al s 3Fe s + Al2O3 s (6)
4. 270-600C 1.8% and boehmite in the red mud,
5. 600-660C 1.1% Formation of diaspora, Addition of these reactions, iron oxide (FeO) from
6. 660-780C 2.8% Melting of aluminium and the decomposition of iron aluminate (FeAl2O4), can react with
7. 780-900C 2.8% decomposition of calcite metallic aluminium in the system.
8. 900-1000 7.1% ,Total weight lost was 7.1%
9. 1000-1100 2.0% Removal of oxygen content 3FeO (FeAl2O4 s (in red mud)+ 2Al s 3Fe s + Al2O3 s (7)
Total 25-1100C 19.2% from the ferric oxides as a
result of the metallization in
the mixture. There is also another possibility of iron oxide (FeO), source in
Total weight loose in the the red mud which is iron titanium oxide. As explained above,
mixture like iron aluminate, It was suggested that, first of all, iron
titanium oxide was decomposed and then reduced to metallic
Differential thermal analysis (DTA) curve of the mixture was iron according to the following reactions;
seen in the Figure 3. As seen from it, there are roughly three
endothermic and two exothermic reaction peaks on the curve. FeTiO5 s (in red mud) FeO s + TiO2 s + O2 g (8)
As seen in the reaction zone 1, the first endothermic peak at
around 260 C corresponds to dehydration of FeO(OH) and 3FeO s (in red mud)+ 2Al s 3Fe s + Al2O3 s (9)
the second at around 660 C represents the melting point of
the added metallic aluminium powder in the mixture (Reaction The determined iron carbide was formed, according to the
2) and the final one at around 860 C could be related to the metallic iron from the reaction 6 and 9 as follows;
formation of iron carbide reaction in the mixture (Reaction
10). The three exothermic peaks at around 780 C, 950 C and Fe(s) + C(s) Fe3C(s) (10)
1100 C represent the reduction of ferric oxides by
aluminothermic reaction. The first exothermic peak is The second reducible ferric oxide is titanium oxide content of
corresponding to the reduction of iron content in the red mud the red mud. It reduces according to the following reaction;
and at temperature between 950-1100 C the reduction of
titanium oxide and silica take place. 3TiO2 s (in red mud)+ 4Al s 3Ti s + 2Al2O3 s (11)
215
A. Atasoy
216
Reduction of Ferric Oxides In The Red Mud by The Aluminothermic Process
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