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6th International Advanced Technologies Symposium (IATS11), 16-18 May 2011, Elaz, Turkey

Reduction of Ferric Oxides In The Red Mud by


The Aluminothermic Process
A. Atasoy
University of Sakarya, Sakarya/Turkey, aatasoy@sakarya.edu.tr

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

T yield considerable masses of solid residues which often


causes environmental and air pollution problems. In the
the disposal of this residue was of much interest.
This study discusses a new aluminothermic process applicable
to the Bayer waste in order to recover valuables such as ferro
case of alumina processing, annual red mud production is
around 66 millions tones in the world[1]. In Turkey at the alloys and other raw materials such as ceramic powders while
Seydiehir alumina refinery, approximately 200, 000 tons of reducing the disposal of this residue. The main advantages of
alumina is produced annually by Bayer process which this process upon the other applications are that, it occurs at
generates around 300, 000 tones/year solid red mud low processing temperatures and the reaction products can
residues[2]. easily be separated by a magnetic method. The results
Previous studies demonstrated that, red mud is a complex obtained from the process and the reaction mechanisms were
material with variable chemical and mineralogical presented in the first part of the paper. The second part of the
composition due to the origin and quality of the bauxite ore work on the production of ceramic powder from the process
and the parameters used during the Bayer process[3-7]. Red will be presented and discussed in another paper. The present
mud can be considered as a secondary raw material paper addressed on several of the relevant parameters and a
particularly for the production of pig iron[8-10], for the combination of physical examination and analysis techniques
production of titanium dioxide[11, 12], a valuable source of has been used to clarify the stages of the reaction mechanism.
rare earth elements[13, 14], as constituent in building
materials[15, 16], ceramic matrices[17-19] and other
applications[20-22]. Recovery of iron in red mud can be done II. EXPERIMENTAL STUDY
by two methods are solid-sate reduction followed by magnetic
separation and smelting operations. A process for the recovery In this work, the aluminothermic reduction of Bayer waste
of iron oxide from red mud by smelting operation proposed. It with the addition of solid carbon was studied. The red mud

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
%

Figure 1: Experimental flow sheet used for the


aluminothermic process of red mud.

Figure 1 shows the material flow chart of the aluminothermic


reduction of the Seydiehir red mud. The production of ferro
alloys by this process involves four stages; 1. Preparation of
the feed by mixing of red mud, carbon and Al powders, 2.
Reduction process, 3. Recovery of the metallic beads by
magnetic separation method, 4. Characterisation of the Figure 2: X-ray pattern of the used sample.
products.
As seen on the above figure, the mixture was placed in a The mineralogical composition of the sample was determined
graphite crucible following the ball milling process and was using X-ray diffraction analysis and is presented in Figure 2.
then heated in electrical furnace at 1000 C for up to three The identified mineral phases in the sample were hematite,
hours. After this reduction stage, the reduced sample was sodium aluminium silicate, calcium aluminium silicate,
crushed and metallic parts were separated by a magnetic bar goethite and gibbsite. The main peaks were labelled in the
of 900 Gauss. figure.
For the determination of mineral in the starting powder and
the reaction phases in the produced metallic beads, X-ray
diffraction method (D/max Rigaku, Japan) was used at the
condition of Cu K radiation (=0.15418 nm) with a step size
of 0.02 (2) and a scanning rate of 2 min-1. Energy
dispersive analytical X-ray (EDAX) was also used for basic
chemical analysis.
Thermal analysis of the mixture was performed on a
simultaneous thermal analyser (Netzsch STA 400, Germany).
TG/DTA was performed in an alumina crucible, under
nitrogen atmosphere in the temperature range of 20-1100 C
and heating rate of 10 C/min.
The generation of chemical, physical and mineralogical Figure 3: Simultaneous TG/DTA curves of the mixture.
properties of the Seydiehir and other red mud samples were
presented by authors previous publications [23-25]. More The simultaneous differential thermal analysis (DTA), thermal
details, regarding the aluminothermic processing of the Bayer gravimetric (TG) and differential thermal gravimetric (DTG)
waste was presented and discussed in the following part of the curves for the mixture of the red mud, carbon and metallic
work. aluminium mixture were presented in Figure 3. As seen from
the TG curve of this mixture, a continuous weight loss has
III. RESULTS AND DISCUSSION occurred between temperatures of 100 and 1100C. The first
wide band was centered at 150 C, this followed by a sharp
The chemical composition of the red mud is presented in peak at 300 C then a plateau at 600 C gave a total weight
Table 1. As seen from the table, the iron oxide content of the loss of 6%; another weight loss characterised by a sharp line
waste is almost half of the total. Under the experimental occurring between 600-660 C and a broad band at 780C;
condition, the oxide content of the red mud sample can be another sharp weight loss occurring in the region of 900 C,
classified into two groups as ferric oxides (Fe2O3, SiO2 and and a faster and very sharp line at 1000C, and a final one
TiO2) and as non ferric oxides (Na2O, Al2O3 and CaO). As above this temperature. The total weight loss is around 19.2%
seen in the chemical composition of the sample, 63% of the in the sample. According to the slope of the TG curve, an

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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)

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A. Atasoy

The last reducible ferric oxide is silica takes place in the


mixture with the following reaction;

3SiO2 s (in red mud)+ 4Al s 3Si s + 2Al2O3 s (12)

X-ray diffraction results of the metallic beads reduced at 1000


C for 1h. was presented in Figure 4. It shows only metallic
iron and iron aluminium silicon compounds. As seen from the
pattern there are numbers of large and small peaks. The major
peaks were marked in the figure. The added Al powder was
reacted totally to reduce the ferrous oxides of the red mud.
Surprisingly metallic aluminium peak was still seen in the
pattern. A comparison of Figs 2 and 4 indicates that there are
large differences between the intensities of the compounds, in
the number of identified peaks, size, shapes and as well as the Figure 5: Optical micrograph of a rigid block after the
products. Any phases which were determined in the starting process.
powder were disappeared in the reduced sample pattern. It
shows that they were reduced to metallic forms. Figure 5 shows polished sections of the reduced sample. It is
clearly visible on the polished section of the sample, there are
three areas which are white, darker and creamy. A creamy
oxide film layer was covered all around the reduced sample.
The white areas are in spherical forms are changing from 50
micron to 6 mm diameter. They are metallic reaction product.
There are uniform metallic particle distribution on the
micrograph which shows all ferric oxides were reduced to Fe,
FeAlSi and Fe3C. At longer holding time, these metallic parts
are collected at the bottom of the crucible in one piece of
metal and the slag was collected at the top of the melted part.
The darker areas represent the new formed oxide during the
process.
Figure 4: X-ray pattern of the produced metallic beads after The basic chemical analysis of the metallic beads was
the process. presented in Table 3. As seen from the table, the product was
almost iron or it can be called iron compounds, since carbon
Density, colour, morphology and particle size of the starting content is in the form of iron carbide. Metallic silicon was
powder are important parameters for determination of the determined in the form of iron aluminium silicon, but titanium
physical properties of starting materials as well as the reaction was not found in the metallic product. The EDS pattern of the
product. The colour of the mixture was changed from grey to metallic part was presented in Figure 6. As seen from it, the
black with the addition of carbon. At the end of the process, intensities of the peaks are good agreement with the chemical
the loose form of the mixtures was changed to rigid block. composition of the sample.
There were spherical metallic beads in different sizes of -6
mm in the reduced sample. The change in the colour of the Table 3: Elemental analysis of the obtained metallic beads
sample is due to the decrease of iron oxide content or the after the process.
reduction of it, in another word, any reduction of the ferrous
oxides was resulted in the change of the colour of the sample. Elements C Fe Al Si Total
After the crashing and the grounding operations, the metallic Wt. % 7.12 87.16 0.67 5.05 100..00
part was separated from the un-reduced oxides in the starting
powder. It is noteworthy that, the density of the mixture was
increased from 3.10 to 6.56 gr cm-3 after the aluminothermic
reduction process. It was resulted due to the formation of new
metallic phases with higher densities.
Surfaces, particle morphology of the starting materials play an
important role during the aluminothermic process. The
average particle size of the red mud and solid carbon was 10
micron and 30 micron for metallic aluminium powder. At the
end of the process the bulk powder form was resulted in very
hard form of the reaction product.

Figure 6: EDS pattern of the elements in the metallic beads

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Reduction of Ferric Oxides In The Red Mud by The Aluminothermic Process

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