processes

Article
Characteristics of Bauxite Residue–Limestone Pellets as
Feedstock for Fe and Al2O3 Recovery
Manish Kumar Kar * and Jafar Safarian

Department of Materials Science and Engineering, Norwegian University of Science and Technology (NTNU),
7041 Trondheim, Norway
* Correspondence: manish.k.kar@ntnu.no

Abstract: Experimental research was carried out to produce pellets from bauxite residue for the
further extraction of iron and alumina. Bauxite residue and limestone with three different mixture
compositions were pelletized experimentally via agglomeration followed by drying and sintering
at elevated temperatures. X-Ray diffraction (XRD) and scanning electron microscopy (SEM) were
used for the phase and microstructural analysis, respectively. Tumble, abrasion, and breaking
load tests were applied to determine the strength of the pellets. For measurement of porosity and
surface area, mercury porosimetry and BET surface area methods were applied. It was found that at
1100 ◦ C sintering temperature, all the three sintered pellet compositions have a moderate porosity
and low strength, but the reverse result was found when 1200 ◦ C sintering temperature was applied.
Moreover, for the pellets sintered at 1150 ◦ C high strength and proper porosities were obtained.
In the sintered pellets, iron present in form of brownmillerite (Ca2 Fe1.63 Al0.36 O5 ), srebrodolskite
(Ca2 Fe2 O5 ), and fayalite (Fe2 SiO4 ), while alumina present mostly in gehlenite (Ca2 Al2 SiO7 ) and
little fraction in mayenite (Ca12 Al14 O33 ) and brownmillerite phases. The identified phases are the
same for of the three pellets, however, with variations in their quantities. Porosity and mechanical
properties of pellets are inversely related with both varying sintering temperature and composition.
It was found that with more CaCO3 use in pelletizing, higher porosity is obtained. However, with
increasing sintering temperature the strength of the pellets increases due to clustering of particles,
while porosity decreases.

Citation: Kar, M.K.; Safarian, J.

Keywords: bauxite residue; pelletization; sintering; tumble; abrasion; porosity; strength
Characteristics of Bauxite
Residue–Limestone Pellets as
Feedstock for Fe and Al2 O3 Recovery.
Processes 2023, 11, 137. https://
doi.org/10.3390/pr11010137
1. Introduction
Bauxite residue (BR) is a solid waste generated from the Bayer process during alumina
Academic Editors: Elsayed
production after the significant removal of water from red mud [1,2]. Iron contained in the
Elbeshbishy and Farokh Laqa Kakar
BR is high and usually around 28 to 54 wt.% depending on the origin of the bauxite ore
Received: 22 November 2022 and the Bayer process parameters [2–4]. About 1 to 1.12 tons of BR is generated per ton of
Revised: 23 December 2022 alumina produced [5]. More than 168 million tons of BR is generated globally [6], which is
Accepted: 30 December 2022 a big environmental concern for the aluminum industry because of its large requirement of
Published: 3 January 2023 land for storage and its hazardous nature [3]. It was estimated that the global directory of
BR in 2018 exceled above 4.6 billion tons and stockpiled [7]. The residue is hazardous due
to its high alkalinity, presence of toxic elements, and very fine particle size, which makes the
safe disposal of the residue a big problem. Red mud is stored in huge ponds, which not only
Copyright: © 2023 by the authors.
occupies large land but also pollutes soil, groundwater, and air [8]. However, BR stockpiling
Licensee MDPI, Basel, Switzerland.
is easier as it does not have potential flood accidents, while landfilling must be done via
This article is an open access article
specific precautions in suitable geographical locations. As BR contains a large percentage of
distributed under the terms and
conditions of the Creative Commons
iron, iron recovery from the BR will decrease nearly half the residue’s mass, and a couple of
Attribution (CC BY) license (https://
techniques have been studied in the literature [9–11] through carbothermic reduction [12].
creativecommons.org/licenses/by/ The valorization of BR through carbothermic reduction with simultaneous slag feedstock
4.0/). production for alumina recovery has been studied through the Ensureal EU project [13].

Processes 2023, 11, 137. https://doi.org/10.3390/pr11010137 https://www.mdpi.com/journal/processes

Processes 2023, 11, 137 2 of 18

The carbothermic reduction-based processes have significant carbon footprints and there
are concerns about their application in future. Biocarbon use in the BR valorization has
been tested successfully in lab and pilot scale in Ensureal to establish a new integrated
sustainable process [13].
BR contains iron, aluminum, silicon, calcium, titanium, etc., in different compounds
of oxide, hydroxide, carbonate, etc. These are the major contents, and rare earth elements
(REEs) usually co-exist as minor valuable elements [14]. Significant research and pilot-scale
trials have been carried out in recent years, and still, the commercial utilization of BR in
view of material recovery is a major challenge. However, BR is valorized in small amount
in cement production, and construction. It can be used to make bricks, tiles, and aggregate
blocks for the construction industry, and some patents have been filed [15,16]. The use of
BR in these applications is accompanied with the direct loss of valuable materials [4], in
particular iron, alumina, and REEs, and indeed its valorization in metallurgical industry is
important with regard to circular economy.
A sustainable approach to valorize BR and extract iron, alumina, and REEs has been
recently introduced by HARARE EU project, in which an approach to hydrogen reduction
of BR agglomerate is carried out to form metallic iron, followed by its magnetic separation
and further alumina and REE extraction from the non-magnetic portion. The present
research is about the production of feed material for the HARARE process in a so-called Ca-
route in which the agglomeration of BR is conducted via mixing with a significant amount
of CaO or CaCO3 . The addition of lime to BR is based on former research results for Al2 O3
recovery from calcium aluminate slags [17] and to stabilize leachable Al2 O3 -containing
phases in the reduced pellets. Azof et al., 2019 found that the leachability order of the
calcium aluminate phase from lowest to highest is as follows CaO.Al2 O3 , 3CaO.Al2 O3
and 12CaO.7Al2 O3 [17]. When 7 moles of alumina combines with 12 moles of calcium
oxide, mayenite is formed (12CaO.7Al2 O3 ), which is an easily leachable phase in Na2 CO3
solution to form sodium aluminate and calcium carbonate residue [18,19]. The goal of
CaCO3 addition is to form leachable calcium aluminate phases and iron calcium complexes
containing as little as possible of the non-leachable gehlenite (Ca2 Al2 SiO7 ) phase. In this
paper, we focused on the chemical, physical, structural, and mechanical properties of
BR–lime pellets based on the limestone fraction and applied sintering temperature.

2. Materials and Methods

2.1. Materials Preparation
BR was provided by the Mytilineos Metallurgy Business Unit S.A., which was pre-
viously named Aluminum of Greece, in the form of large and hard lumpy pieces. These
were first deagglomerated into a fine powder and dried overnight in an oven at 80 ◦ C.
Limestone was received from a paper manufacturing plant in Norway as a waste prod-
uct, and it was dried for two days in the oven at 80 ◦ C. After the limestone was dried, it
was deagglomerated into a fine powder with particle size around the same as BR, below
500 µm.

2.2. Pelletizing and Sintering

The two raw material powders were mixed in three different CaO/Al2 O3 ratios equal
to 0.85, 1.0, and 1.15 (called hereafter C0.85 A, C1 A, and C1.15 A, respectively) in a ball
milling machine at 30 revolutions per minute (rpm) for 90 min to do both mixing and
deagglomerate possible remained large BR or limestone clusters. The mixing ratio selection
was based on the chemical composition of the two materials and maintained the formation
of leachable calcium aluminates in the pellets. Green pellets were produced using a disk
pelletizer via water addition. The pelletizing disk speed was 26 ± 2 rotations per minute
(rpm) with the disk volume capacity around 130 dm3 , and the disc angle was 45 degrees,
as experienced to be the optimum angle. The size of the produced green pellets was
4–10 mm, and the pellets were dried in an oven overnight at 80 ◦ C. The overall flow process
of pelletization and further high-temperature sintering is shown in Figure 1.
Processes 2023, 11, x FOR PEER REVIEW 3 of 18

Figure 1. Overall pelletization and sintering process.

Processes 2023, 11, 137 mm, and the pellets were dried in an oven overnight at 80 °C. The overall flow process
3 of 18 of
Sintering and
pelletization has further
two main roles; one is sintering
high-temperature to form issome complexes,
shown and the other is to
in Figure 1.
strengthen pellets. Pellet strength has prime importance for the bed permeability; other-
wise, it hinders the homogenization of gas flow through the solid bed, which ultimately
affects the gas–solid reaction. The dried pellets were subjected to high-temperature sin-
tering in a muffle furnace (Naberthem N17/HR, Bremen, Germany) at three different tem-
peratures (1100 °C, 1150 °C, and 1200 °C) in air. The heating rate of the furnace was 25
°C/min to the desired temperature, 120 min of holding time at the sintering temperature
followed by sample cooling in the furnace. After sintering, the color of the pellets changed
from brown to black, as typically shown for increasing temperature for pellet C1A in Fig-
ure 2. As shown in Figure 2, there is some clustering of the pellets at C1A-1200 °C sintered
pellets with possible partial fusion or formation of semi-molten species. In the C1A-1100
°C- and C1A-1150 °C-sintered pellets, no clustering was observed, while for the latter, the
Figure 1. Overall
pellets pelletization and sintering process.
Figurewere stronger
1. Overall with no
pelletization andbreakage in handling, which was observed for the pellets
sintering process.
C1A-1200 °C as well.
Sintering has two main roles; one is to form some complexes, and the other is to
Sintering
In commercial
strengthen has iron
pellets. two main
Pelletore roles;
has one
pelletizing
strength prime isimportance
to formsuch
machines some thecomplexes,
for as grate–kiln, and the
the pellets
bed permeability; other
areisheated
otherwise, to
tostrengthen
high
it hinders pellets.
temperatures Pellet
andstrength
the homogenization cooled has
down
of gas prime
flow importance
in continuous
through for
bed,the
the solidprocess, bed
whichand permeability;
the residence
ultimately other-
affects at the
wise,
the it hinders
gas–solid the homogenization
reaction. The dried of
pellets gas
were flow through
subjected to the solid bed,
high-temperature
elevated temperatures may be shorter than the selected heating profile in this study. How- which ultimately
sintering in
a muffle
affects thefurnace
gas–solid(Naberthem
reaction. N17/HR,
The dried Bremen,
pellets Germany)
were at three different
subjected temperatures sin-
to high-temperature
ever, as the produced pellet ◦compositions in this study are new the chosen temperature
(1100in◦ C,
tering a 1150 ◦ C,
muffle and 1200
furnace C) in air. The
(Naberthem heating
N17/HR, rate of the
Bremen, furnace at
Germany) was 25 ◦different
three C/min totem-
profile was to temperature,
the desired
achieve an 120 overview
min of
of temperature
holding
effect. Ontemperature,
the other hand, in the real
peratures (1100 °C, 1150 °C, and 1200 °C) intimeair.atThe
the heating
sinteringrate followed
of the furnace was 25
pelletizing machine there is flow of warm and hot gases through
by sample cooling in the furnace. After sintering, the color of the pellets changed from the pellets bed (in differ-
°C/min to the desired temperature, 120 min of holding time at the sintering temperature,
ent direction)
brown to black, andasvery complicated
typically shown forthan the applied
increasing temperaturesimple for sintering
pellet C1 A in Figure
the muffle
2. fur-
followed by sample cooling in the furnace. After sintering, the color of ◦ Cthe pellets changed
As shown in Figure 2, there is some clustering of
nace in this study. An important outcome of this study is, however,the pellets at C 1 A-1200 sintered pellets
that maximum sinter-
from
withbrown to black,
possible partial as typically
fusion or shown for
formation increasing
of pellets.
semi-molten temperature
species. the for pellet
In the C1A◦in
C1 A-1100 C- Fig-
ing temperature
ure 2. As shown◦inof 1150 °C is proper
Figure 2,pellets,
there isno for
some BR clustering Optimizing proper heating regime
and C1 A-1150 C-sintered clustering was of the pellets
observed, at C
while 1A-1200 °C sintered
for the latter, the
and even under
pellets gas flows tofusion simulate real pelletizing machine needsIn dedicated experi-
pelletswith
werepossible
strongerpartial
with no breakage or formation
in handling, of which
semi-molten species.
was observed for thethepellets
C1A-1100
mental
°C-
C and further
A-1200 ◦ C research.
C1A-1150 °C-sintered pellets, no clustering was observed, while for the latter, the
as well.
1
pellets were stronger with no breakage in handling, which was observed for the pellets
C1A-1200 °C as well.
In commercial iron ore pelletizing machines such as grate–kiln, the pellets are heated
to high temperatures and cooled down in continuous process, and the residence at the
elevated temperatures may be shorter than the selected heating profile in this study. How-
ever, as the produced pellet compositions in this study are new the chosen temperature
profile was to achieve an overview of temperature effect. On the other hand, in the real
pelletizing machine there is flow of warm and hot gases through the pellets bed (in differ-
ent direction) and very complicated than the applied simple sintering in the muffle fur-
nace in this study. An important outcome of this study is, however, that maximum sinter-
ing temperature of 1150 °C is proper for BR pellets. Optimizing the proper heating regime
and even under gas flows to simulate real pelletizing machine needs dedicated experi-
mental further research.
Figure
Figure 2. Sintered
2. Sintered oxidepellets
oxide pellets at
at different
differenttemperatures for Cfor
temperatures 1 A.C1A.

In commercial iron ore pelletizing machines such as grate–kiln, the pellets are heated to
high temperatures and cooled down in continuous process, and the residence at the elevated
temperatures may be shorter than the selected heating profile in this study. However, as
the produced pellet compositions in this study are new the chosen temperature profile was
to achieve an overview of temperature effect. On the other hand, in the real pelletizing
machine there is flow of warm and hot gases through the pellets bed (in different direction)
and very complicated than the applied simple sintering in the muffle furnace in this study.
An important outcome of this study is, however, that maximum sintering temperature of
1150 ◦ C is proper for BR pellets. Optimizing the proper heating regime and even under gas
flows to simulate real pelletizing machine needs dedicated experimental further research.

Figure 2. Sintered oxide pellets at different temperatures for C1A.

Processes 2023, 11, 137 4 of 18

2.3. Characterization
The mineralogical analysis of materials was carried out by X-Ray diffraction (XRD)
technique (Bruker D8 A25 DaVinciTM, Karlsruhe, Germany) with the CuKσ radiation in
2θ range from 20 to 70◦ diffraction angle and step size 0.03 degrees. For the diffraction
analysis, the pellets were milled to a fine powder in the ring mill for 45 s at rpm 800. For
the phase analysis, a crystallographic database and diffraction EVA software were used.
The elemental analysis of the raw materials and produced pellets were conducted using the
X-Ray fluorescence (XRF) technique (Thermo Fisher, Degerfors labortorium AB, Sweden).
For the microstructural analysis of materials, a scanning electron microscope (SEM) (Zeiss
ultra 55LE, Carl Zeiss, Jena, Germany) was used. The chemical elements distribution was
evaluated using elemental mapping and energy dispersive spectroscopy (EDS) (Bruker
AXS, microanalysis GmbH, Berlin, Germany).
The porosity and pore size distribution of pellets were measured by a mercury in-
trusion porosimeter (Autopore IV 9520, Micromeritics, USA ) applying high pressures.
BET surface area was measured using 3Flex 3500 Chemisorption Analyzer, Micromeritics,
USA. Before the sample analysis, the sample was degassed at 250 ◦ C for 10 h to remove
the moisture contents of the sintered pellets. To check the strength of the pellets, we used
a Compact Hydraulik press, and the cold compression strength of a few single pellets was
measured, and the average was calculated. Three measurements for each pellet were car-
ried out to take the average for the calculation of the breaking load. Tumbler and abrasion
tests were done as per international standard ISO 3271, 3rd edition [20]. For this test, we
used pellets of size greater than 7 mm in diameter in a mini-tumbler test unit in which
the standard [20] is rescaled to a smaller size. The dimension of the mini tumbler was
an inner diameter of 200 mm, 12 mm in length, and a lifter drum height of 6 mm. The
rotation speed of tumbler was 40 rpm for 30 min and 1200 total revolution. The abrasion
index was calculated based on the weight fraction of fines below 500 µm divided by the
total weight of pellets which is 50 g. The tumble index was calculated as the weight frac-
tion above 5.5 mm pellets divided by the total weight of the pellets taken for the testing.
The true density of pellets was measured by a pycnometer (Micromeritics, Accupyc 1340,
Pycnometer, USA) with helium gas injection. The calculated true density was based on the
total mass divided by the true volume of the sample.

3. Results
3.1. Physical Properties
All the physical properties of the pellets mentioned above are presented and described
as follows. The mass loss of all the pellets was in the range of 21 to 23.8% during sintering,
as shown in Table 1. The mass loss was more for the more added CaCO3 pellets. With
increasing temperature, the weight reduction increases, but there was a smaller weight
reduction difference between 1150 ◦ C and 1200 ◦ C.

Table 1. Weight reductions (wt.%) at different applied sintering temperatures.

Composition/Temperature (◦ C) 1100 ◦ C 1150 ◦ C 1200 ◦ C

C0.85 A 21.4 21.6 21.8
C1 A 21.5 21.8 21.9
C1.15 A 23.1 23.7 23.8

The BET surface area of dried pellets of C1 A is around 16.6 m2 /g, while the sintered
pellets have a lower surface area. Table 2 shows the BET surface area and porosity of C1 A at
different sintering temperatures. With increases in sintering temperature, both BET surface
area and porosity decrease at fixed composition of C1 A.
Processes 2023, 11, 137 5 of 18

Table 2. BET surface area and porosity of different sintering temperatures for C1 A.

Temperature (◦ C) BET Surface Area (m2 /g) Porosity (vol%)

1100 1.06 58.85
1150 0.29 54.99
1200 0.25 31.45

Table 3 shows the BET Surface area and porosity of pellets sintered at 1150 ◦ C for
different compositions. With an increase in CaCO3 in pelletizing at the fixed sintering
temperature, both BET surface area and porosity are increased.

Table 3. BET surface area and porosity of different composition (CX A) pellets at 1150 ◦ C sintering.

Composition (CxA) BET Surface Area (m2 /g) Porosity (vol%)

C0.85 A 0.25 43.35
C1 A 0.29 54.99
C1.15 A 0.39 66.78

For a given pellet composition C1 A, it was observed that the sintering temperature
rise causes the true density to increase. The density is around 3.53 g/cm3 for 1200 ◦ C and
3.52 g/cm3 for 1150 ◦ C sintered pellets, which is not notable. Standard drop number test
was carried out, where green pellets were individually dropped from a 46 cm height on
a thick steel plate until the pellets had a breakage or crack appearance on the surface. It was
found that drop numbers were the same and in the range of four to five for three different
types of green pellets. The wet crushing strength of all three pellet compositions was
performed by compression test instrument and found around 0.009–0.01 kN, which were
near around compact strength of dry pellets (about 0.01 kN). There was no observation
of swelling and no disintegration during the sintering of the pellets, which is shown in
Figure 2, which signifies the pellets are not deformed at sintering temperature. Table 4
shows that the breaking load for the sintered pellets increases with increasing the sintering
temperature. In addition, an increase in the CaCO3 content of the pellets is accompanied
by breaking load decreases.

Table 4. Breaking load of different sintering temperature with different pellets composition. (All
measurements in kN, SD: standard deviation).

Ratio/Temperature 1100 ◦ C 1150◦ C 1200◦ C

C1.15 A 0.0133 0.05 0.5
SD 0.01 0.01 0.1
C1 A 0.0366 0.2933 0.8166
SD 0.01 0.08 0.8
C0.85 A 0.0733 0.4466 1.266
SD 0.02 0.04 0.08

In a gas–solid reaction, the strength of the pellets bed is very important to have low
pellet degradation and abrasion and attain proper gas flow. For C1 A-1150 ◦ C, C1 A-1200 ◦ C,
and C0.85 A-1150 ◦ C pellets, the tumble index was above 88%, and the abrasion index was
below 6% (see Figure 3), which showed good strength of the pellets for further handling.
The tumbler index is around 80%, and abrasion index is around 10% for C1.15 A-
1150 ◦ C sintered pellets. It was found in the literature that a tumble index above 92% and
an abrasion index below 6% show quite good strength for iron ore pellets for the Midrex
process [21]. For C1 A-1100 ◦ C, the tumble index is around 54% and abrasion index is
around 14%, which signifies this pellet does not have good strength.
Processes2023,
Processes 2023,11,
11,137
x FOR PEER REVIEW 66 of 18
of 18

Figure 3.
Figure 3. Tumble
Tumble and
and abrasion
abrasion indexes
indexes of
of sintered
sinteredpellets.
pellets.

3.2.
3.2. Chemical
Chemical Analysis
Analysis
The chemical analysisof
The chemical analysis ofthe
thematerials
materialswith
withXRF
XRF is is presented
presented in in Table
Table 5. XRF
5. XRF gavegave
the
the results in the form of elemental analysis, but here we presented the
results in the form of elemental analysis, but here we presented the most stable oxidemost stable oxide
forms
forms ofof those
those elements.
elements. TheThe XRF
XRF results
results show
show that
that the
the loss
loss of
of ignition
ignition (LOI)
(LOI) was
was high
high for
for
limestone
limestone sample, as limestone contains CO22 in calcite that is decomposed. The LOI was
sample, as limestone contains CO in calcite that is decomposed. The LOI was
around
around 22.5%
22.5%for fordry
drypellets,
pellets,and
andit was below
it was below1%1%for for
the the
sintered pellets.
sintered The The
pellets. relative loss
relative
weight percentage (wt.%) of oxides is more in the sintered pellets as compared to the dry
loss weight percentage (wt.%) of oxides is more in the sintered pellets as compared to the
pellet, which is due to higher LOI in the case of dry pellets, but Na2 O content decreases,
dry pellet, which is due to higher LOI in the case of dry pellets, but Na2O content de-
which indicates that there is some Na2 O loss during sintering, probably due to lower vapor
creases, which indicates that there is some Na2O loss during sintering, probably due to
pressure than other oxides.
lower vapor pressure than other oxides.
Table 5. Chemical composition of different materials measured by XRF (wt.%).
Table 5. Chemical composition of different materials measured by XRF (wt.%).
Samples/Oxides
Samples/Oxides Al2OAl3 2 OCaO
3 CaO Fe2OFe
3 2O K32O KMnO
2O MnO
MgOMgO Na2ONa2P O2O5 P2SO
O5 3 SO 3 2SiO
SiO 2 TiO
TiO 2 2 2Cr
Cr O32 O3 VV22O
O55 NiO
NiO LOI
LOI
BRBR 22.0022.008.80 8.8041.7141.710.09 0.09
0.08 0.08
0.23 0.233.10 3.100.11 0.11
0.95 0.95
6.10 6.105.005.00 …... . . …..
... .…..
.. 11.83
11.83
Limestone
Limestone 0.90 0.9052.7052.700.15 0.150.12 0.12
….. . .0.95
. 0.95….. . . .0.01 0.01
0.06 0.06
2.07 2.070.030.03 ……... ...
….. .…..
.. 42.60
42.60
BR + CaCO3
BR(Dry
+ CaCO 3
pellets)
13.20 27.50 23.20 0.15 0.04 0.59 2.55 0.07 0.58 6.05 3.25 0.14 0.11 0.07 22.40
13.20 27.50 23.20 0.15 0.04 0.59 2.55 0.07 0.58 6.05 3.25 0.14 0.11 0.07 22.40
(DrySintered
pellets)
◦ 19.80 32.80 29.60 0.19 0.05 0.51 2.31 0.12 0.96 8.30 4.07 0.20 0.15 0.10 0.72
(C 1 A-1150 C)
Sintered
19.80 32.80 29.60 0.19 0.05 0.51 2.31 0.12 0.96 8.30 4.07 0.20 0.15 0.10 0.72
(C1A-1150 °C)
3.3. Phase Analysis (XRD)
3.3. Phase Analysis (XRD)
XRD analysis result of BR and limestone is shown in Figure 4. Iron is present in
the BRXRD analysis
in the form result of BR (Fe
of hematite and2 O limestone is shown in Figure 4. Iron is present in the
3 ) and goethite (FeHO2 ). Titanium is present in the
form of anatase (TiO2 ) and perovskite (CaTiO3 ).(FeHO
BR in the form of hematite (Fe 2 O 3 ) and goethite Calcium 2). Titanium
appearsisaspresent
a calcitein (CaCO
the form 3)
of anatase (TiO ) and perovskite (CaTiO ). Calcium
phase in the BR. Aluminum presents as diaspore σ-AlO (OH) and complex phases
2 3 appears as a calcite (CaCO 3 ) phase in
such
thesodalite
as BR. Aluminum
(Al3 Cl1 Kpresents
1 Na4 O12asSi3diaspore
), cancrinite ꭤ-AlO (OH)
(C0.76 H1.7and
Al3complex
Ca0.75 Naphases such
3 O14.4 Si as sodalite
3 ), and katoite
(Al3Cl31H
(AlCa K19.7
Na OSi
O412 12Si3),). The
0.69 cancrinite
XRF analysis (C
in H
Table
0.76 1.7Al
5 Ca 0.75Na
3shows 3O14.4
that Si 3),
hematite and
present inkatoite
BR is
(AlCa3H42%,
around 9.7O12which
Si0.69). The
is theXRF
majoranalysis
phase,in and Table
alumina5 shows that hematite
is around 22%, which present in BR is
is undigested
around 42%,
alumina; hence which is the major
the quantity phase, and alumina
of Al-containing phases in is the
around 22%,
sample which isXRD
regarding undigested
results
is higher. Calcium in XRF analysis of the limestone is usually reported as CaO. results
alumina; hence the quantity of Al-containing phases in the sample regarding XRD In the
is higher. sample,
limestone Calciumthe in XRD
XRF spectrum
analysis of the limestone
contains only CaCO is usually
3 , whilereported as CaO.a In
in XRF analysis, the
small
limestone
amount of sample, the XRD
Al2 O3 , MgO, spectrum
Fe2 O contains
3 , SiO2 , etc., wereonly CaCO3, while in XRF analysis, a small
measured.
amount of Al2O3, MgO, Fe2O3, SiO2, etc., were measured.
Processes 2023,11,
Processes2023,
Processes 2023, 11,137
11, xxFOR
FORPEER
PEERREVIEW
REVIEW 7 7ofof 18
18
18

Figure 4.XRD
Figure XRD patternsof
of the bauxite
bauxite residue and
and limestone with
with the identified
identified phases.
Figure 4.
4. XRD patterns
patterns of the
the bauxite residue
residue and limestone
limestone with the phases.
the identified phases.

XRDresults
XRD resultsof
results ofthree
of threesintered
three sintered
sintered temperatures
temperatures
temperatures for
forfor pellet
pellet
pellet C1 AC11are
C A are
A are illustrated
illustrated
illustrated in
in Figure
in Figure 5. It5.
Figure 5.
is
It
shown
It is shown that
that there
is shown that therethere are
are notable notable phase
phase changes
are notable changes
phase changes betweenbetweenbetween
the sinteredthe sintered
pellets and
the sintered pellets and
and raw
raw materials
pellets raw
materials
(Figure
materials (Figure
4).(Figure
Iron is mostly 4). Iron
4). Iron is mostly
present
is mostly present
in thepresent
sinteredin inpellets
the sintered
the sintered pellets as
as brownmillerite
pellets as (Cabrownmillerite
2 (Fe,Al)2 O5 ),
brownmillerite
(Ca 2(Fe,Al)2O5),
srebrodolskite (Ca srebrodolskite
(Ca2(Fe,Al)2O5), srebrodolskiteFe
2 2 5 O ), and (Ca 2Fe2O(Fe
fayalite
(Ca2Fe2O5), and 5), and
2 SiO fayalite
). The
fayalite
4
(Fe
main 2SiO 4). The
other main
phases
(Fe2SiO4). The main other inother phases
the sintered
phases
in
in the
pellets sintered
are gehlenite
the sintered pellets
pellets (Ca are
are gehlenite
2 Algehlenite
(Ca
2 SiO7 ), cristobalite
2 Al
(Ca2Al2SiO 2 SiO(SiO
7 ), cristobalite
2 ), perovskite
7), cristobalite
(SiO
(SiO ),
(CaTiO
2 perovskite (CaTiO
3 ), lime (CaO),
2), perovskite (CaTiO 3),
and
3),
lime
yeelimite
lime (CaO),
(CaO), (Aland
and yeelimite
6 Cayeelimite
4 O16 S). XRD
(Al
(Al6Ca6 Ca
shows4 O 16
4O16S).
S). XRD
some
XRD freeshows
CaOsome
shows some
presentfree CaO
freeinCaO present
the present in the
sinteredinpellets, sintered
while
the sintered
pellets,
the whileofthe
intensity
pellets, while the
free intensity
CaO is less
intensity of free
of free aCaO
for CaO is less
higher
is less for aa higher
sintering
for higher sintering
temperature
sintering temperature
of 1200 ◦ C compared
temperature of
of 1200
1200 to
°C
°C compared
a lower sintering
compared to a lower
to a temperature. sintering
lower sintering The temperature.
brownmillerite
temperature. The
The(Ca brownmillerite
2 (Fe, Al)2 O5 )(Ca
brownmillerite (Ca (Fe,
phase
2
2(Fe,
Al)
has
Al)the
2O
2O5)
5 ) phase
highest
phase
hasthe
amount thehighest
highest ◦amount
at 1150 amountC sinteringat 1150
1150 °C sintering
sintering temperature.
temperature. temperature.
has at °C

Figure5.
Figure 5. XRD
XRD patterns
patterns of
of the
the C
C11A
A oxide
oxide pellets
pellets at
at different
different sintering
sintering temperatures.
temperatures.
Figure 5. XRD patterns of the C 1A oxide pellets at different sintering temperatures.
Processes 2023,
Processes 2023, 11,
11, xx FOR
FOR PEER
PEER REVIEW
REVIEW 888 of
of 18
18
Processes 2023, 11, 137 of 18

The XRD
The
The XRD spectrums
XRD spectrums
spectrumsfor for the
forthe theC1.15
C A and
1.15A
C1.15 and C0.85
C
A and 0.85AA are
C are presented
presented in in Figures
Figures 66 and
and 7,7, respec-
respec-
0.85 A are presented in Figures 6 and 7,
tively. In
tively. In both
bothIn
respectively. mixtures,
mixtures, the identified
the
both mixtures, identified phases are
phases
the identified are almost
almost
phases the
arethe same,the
same,
almost butsame,
but the main
the main difference
butdifference
the main
is adding a different
is adding aisdifferent amount
adding aamount of CaCO
CaCO3. The
of amount . The perovskite
perovskite (CaTiO ) peak appears differently.
3 . The (CaTiO 3) peak appears differently.
3 3
difference different of CaCO perovskite (CaTiO 3 ) peak appears
In the
In the lower
lowerInCaCO
differently. CaCO addition,
33 addition,
the lower CaCOthe the perovskite
perovskite
addition, the (CaTiO33)) peak
(CaTiO
perovskite peak intensity
intensity
(CaTiO ) peakisintensity
is strongeris
stronger atstronger
at 1100 °C
1100 °C
3 3
than
than
at 1150
◦
1150
1100 °C,
C °C, while
thanwhile ◦it
1150 itC, again
again becomes
whilebecomes stronger
it again stronger
becomes at at the higher
the higher
stronger sintering
at thesintering temperature
temperature
higher sintering of 1200
of 1200
temperature
°C1200
°C
of (Figure
(Figure 7).
◦ C 7). However,
However,
(Figure for the
for
7). However, the higher
higher CaCO
for theCaCO higher addition,
33 addition, the perovskite
the
CaCO3 addition, perovskite (CaTiO33)) spectrum
(CaTiO
the perovskite spectrum
(CaTiO3 )
is stronger
is strongerisat
spectrum at higher at
higher
stronger temperatures.
temperatures.
higher temperatures.Iron-containing
Iron-containing phases behave
phases
Iron-containing behave similarly
phasessimilarly at different
at different
behave similarly at
sintering
different temperatures
sintering sintering
temperatures in higher
in higherin
temperatures and
and lower
lower
higher CaCO
CaCO
and lower ratios.
3 ratios.
3
CaCOAt At 1150
1150 °C,
3 ratios.
°C, sintering
Atsintering ◦ tempera-
tempera-
1150 C, sintering
ture iron-containing
ture iron-containing
temperature phasesphases
phases
iron-containing in all
in all three
three pellets
pellets
in all three compositions
compositions
pellets compositions havehave
have aa higher
higher
a higherintensity
intensity of
of
intensity
peaks
peaks
of peaksas compared
as as
compared
compared to
to toother
other sintering
sintering
other sintering temperatures.
temperatures.
temperatures.

Figure 6.
Figure
Figure 6. XRD patterns of
6. of the
the C
C1.15
1.15A
1.15 A oxide
Aoxide pellets
oxidepellets at
pelletsat different
atdifferent sintering
different sintering temperatures.
sintering temperatures.
temperatures.

Figure 7.
Figure 7. XRD
XRD patterns
patterns of
of the
the C
C0.85
0.85A oxide
Aoxide pellets at different sintering temperatures.
0.85A oxidepellets
pelletsat
atdifferent
different sintering
sintering temperatures.
temperatures.
11, x FOR PEER REVIEW 9 of 18

From the XRD spectrums in Figures 5–7 for all pellets at 1150 °C sintering tempera-
ture, it is observed that the iron-containing phases of brownmillerite (Ca2(Fe,Al)2O5), sre-
Processes 2023, 11,
From the XRD spectrums in Figures 5–7 for all pellets at 1150 °C sintering tempera-
137
brodolskite (Ca2Fe2O5) and fayalite (Fe2SiO4) have higher intensity peaks for C1A. Perov- 9 of 18
ture, it is observed that the iron-containing phases of brownmillerite (Ca2(Fe,Al)2O5), sre-
skite (CaTiO3) peak was found to have higher intensity in C1A and C1.15A but the lower
brodolskite (Ca2Fe2O5) and fayalite (Fe2SiO4) have higher intensity peaks for C1A. Perov-
intensity at C0.85A.
skite (CaTiO3) peak wasthefound
From to haveinhigher
XRD spectrums Figuresintensity in C1A
5–7 for all pellets and ◦C
at 1150 C 1.15 A buttemperature,
sintering the lower
intensity at C0.85itA.
is observed that the iron-containing phases of brownmillerite (Ca2 (Fe,Al)2 O5 ), srebrodol-
3.4. Microstructural Analysis
skite (Ca Fe O ) and fayalite (Fe SiO ) have higher intensity peaks for C A. Perovskite
2 2 5 2 4 1
Figure 8 shows
(CaTiO3the
3.4. Microstructural
) peak
Analysis SEMwas images
found to ofhavesintered pellet C
higher intensity A1 A
in1C atand
different temperatures.
C1.15 A but It
the lower intensity
at C
shows that the sintering
0.85 A. of particles is significant at 1200 °C (Figure 8c), which results in
Figure 8
more of the poresshows the
closing. SEM imagesatof1100
Sintering sintered pellet C1A at(Figure
°C is insignificant different8a);temperatures.
compared to It
3.4. Microstructural Analysis
shows
1200 °C,that the moderate
while sintering sintering
of particles is opensignificant at 1200 °C (Figure 8c), whichsintering
results in
Figure 8 shows theand SEM images porosity have
of sintered been
pellet C1 maintained
A at different via
temperatures. It
more
at 1150of °C
the(Figure
pores closing. Sintering atof1100 °C is and
insignificant◦ (Figure 8a);formation
comparedatto
shows8b).that The evidence
the sintering sintering
of particles is significantsemi-molten phase
at 1200 C (Figure 8c), which results in
1200
higher°C,temperatures
while more
moderate
ofisthe sintering
obvious
pores and
regarding
closing. openthe porosity
Sintering at 1100 ◦ Chave
changes been maintained
inisporosity distribution
insignificant (Figure 8a); via
and sintering
shapeto
compared
at
and1150 °C (Figure
observing 1200 8b).
◦ C, The
while
less liberated evidence
moderate
particles atof
sintering sintering
and open
higher and semi-molten
porosity
temperatures. phase formation
have been maintained via sintering at
at
◦ C (Figure 8b). The evidence of sintering and semi-molten phase formation at higher
higher temperatures is obvious regarding the changes in porosity distribution and shape
1150
and observing temperatures
less liberated is obvious
particles regarding
at higher thetemperatures.
changes in porosity distribution and shape and
Openobserving
Pore less liberated particles at higher temperatures. Closed Pore

Open Pore Closed Pore

(a) 1100 °C (b) 1150 °C (c) 1200 °C

(a) 1100
Figure °C secondary electron image
8. SEM (b)of1150
C1A°C (c) 1200
ratio pellets with three different °C tempera-
sintering
tures (a) 1100 °C, (b) 1150 °C, (c) 1200 °C.
Figure 8. SEM secondary electron image of C1 A ratio pellets with three different sintering tempera-
Figure 8. SEM secondary electron image of C1A ratio pellets with three different sintering tempera-
tures (a) 1100 ◦ C, (b) 1150 ◦ C, (c) 1200 ◦ C.
tures (a) 1100 °C, (b) 1150 °C,in(c)
Figure 9 shows that lower C0.85A, too much sintering occurred at 1150 °C, which
1200 °C.
results in lower open porosity
Figure 9 showsinthat
theinpellets
lower C compared to 1100
0.85 A, too much °C (Figure
sintering occurred8).atIn1150
C1.15◦A
C, and
which
◦
C1A samples
Figure 9in Figure
results
shows in 9,
that the
in microstructures
lower open porosity
lower C0.85A,intoo are
the moresintering
pellets
much similar. At
compared to a higher
1100
occurred C atCaCO
(Figure
11508). mixture
3°C,Inwhich
C1.15 A
(C1.15A)in
the and
porosityC A samples in Figure 9, the microstructures are more similar. At a higher CaCO
results lower openisporosity
1 more visible,
in thewhich
pelletsagrees with the
compared above°C
to 1100 porosity
(Figuremeasurements.
8). In C1.15A and3
mixture (C1.15 A) the porosity is more visible, which agrees with the above porosity mea-
The
C SEM backscattered
1A samples Figure 9,images
insurements. theSEM in Figure 9 show
microstructures are that
more the produced
similar. apellets
At that
higher are
CaCO not3homo-
mixture
The backscattered images in Figure 9 show the produced pellets are
geneous regarding
(C1.15A) the porosity the chemical
is more visible,
not homogeneous composition.
which
regarding agrees composition.
the chemical with the above porosity measurements.
The SEM backscattered images in Figure 9 show that the produced pellets are not homo-
geneous regarding the chemical composition.

(a) C0.85A (b) C1A (c) C1.15A

Figure 9. SEM backscattered electron images of three different pellet compositions sintered at 1150 ◦ C
Figure 9. A
(a) C0.85 (a) C0.85 A, (b) Celectron
SEM backscattered 1 A, (c) C1.15 A.
images
(b) Cof
1A (c) Csintered
three different pellet compositions 1.15A at 1150
°C (a) C0.85A, (b) C1A, (c) C1.15A.
From the scanning electron microscopy (SEM) backscattered detector (QBSD) analysis
(Figure 10), it was found that the brightest phases are calcium ferrite (Ca2 Fe2 O5 ), calcium
FigureFrom
9. SEM
thebackscattered
scanning electron
electron images of three
microscopy (SEM) different pellet compositions
backscattered sintered
detector (QBSD) at 1150
analy-
aluminoferrite (Ca2 (Fe,Al)2 O5 ) and calcium titanate (CaTiO3 ). However, the CaTiO3 phase
°C
sis(a) C0.85A,10),
(Figure (b) Cit1A,
was(c) found
C1.15A. that the brightest phases are calcium ferrite (Ca2Fe2O5), cal-
appears brighter in the SEM images, with close contrast. We found that Ca2 Fe2 O5 contains
cium aluminoferrite (Ca2(Fe,Al)2O5) and calcium titanate (CaTiO3). However, the CaTiO3
phase From the scanning
appears electron
brighter in microscopy
the SEM (SEM)
images, with backscattered
close contrast. Wedetector (QBSD)
found that analy-
Ca2Fe 2O5
sis (Figure 10), it was found that the brightest phases are calcium ferrite (Ca 2Fe2O5), cal-
contains a few percentages of aluminum, such as 6.11 at%, representing Ca2Fe1.44Al0.55O5.
cium aluminoferrite (Ca2(Fe,Al)2O5) and calcium titanate (CaTiO3). However, the CaTiO3
Processes 2023,11,
Processes2023, 11,137
x FOR PEER REVIEW 10 of
10 of 18
18

aThe
fewgreypercentages
phase is theof aluminum,
Ca2Al2SiO7 suchphase, asand
6.11the
at%, representing
outer periphery Ca Fe1.44
of 2the Al0.55
gray phaseO5 . isThe
so-
grey phase is the Ca Al SiO phase, and the outer periphery of the
dium aluminate (Figure 10). Silicon is present in two phases in the matrix, one is
2 2 7 gray phase is sodium
aluminate
Ca2Al2SiO7(Figure 10). Silicon
, and another one isisFe
present in two phases in the matrix, one is Ca2 Al2 SiO
2SiO4. As the Fe2SiO4 fraction is low (XRD result), 7,
very
and another one is Fe SiO . As the
small areas show the2EDS4elemental mapping Fe 2 SiO 4 fraction is low (XRD result), very small
of both Fe, Si, and O. Sodium in the matrix areas
show
in sometheareas
EDS elemental
(Figure 10).mapping
Regardingof both
Al, O,Fe,and
Si, and O. Sodium in the
Si co-distribution, it ismatrix in some
confirmed thatareas
they
(Figure
are found in the form of sodium aluminate and jadeite (AlNaO6Si2) phases, and itinis
10). Regarding Al, O, and Si co-distribution, it is confirmed that they are found
the formwith
aligned of sodium
the XRD aluminate
analysisand jadeite (AlNaO6 Si2 ) phases, and it is aligned with the
above.
XRD analysis above.

Al Si

O Fe Ti

Ca Na

Figure 10.EDS
Figure10. EDSelemental
elementalmapping
mappingof
ofCC1.15 A sintered at 1150 ◦ C.
1.15A sintered at 1150 °C.

The elemental analysis in Figure 10 shows that Ca, Al, and Si are found in a phase
The elemental analysis in Figure 10 shows that Ca, Al, and Si are found in a phase
together, most likely the Ca2 Al2 SiO7 phase, considering the XRD results. The elemental
together, most likely the Ca2Al2SiO7 phase, considering the XRD results. The elemental
mapping at 1150 ◦ C sintered C1.15 A pellets shows that in some areas, sodium, and alu-
mapping at 1150 °C sintered C1.15A pellets shows that in some areas, sodium, and alumi-
minum present with high intensity, but calcium is deficient in those areas (Table 6). Calcium
num present with high intensity, but calcium is deficient in those areas (Table 6). Calcium
is distributed everywhere in the matrix but is more intense in the iron-containing area.
is distributed everywhere in the matrix but is more intense in the iron-containing area.
Table 6. EDS elemental analysis of different areas and points of Figure 11a.
Table 6. EDS elemental analysis of different areas and points of Figure 11a.
Elements Area 1 Area 2 Area 3 Point 4
Elements Area 1 Area 2 Area 3 Point 4
Al 35.0 41.1 35.5 31.7
Al 35.0 41.1 35.5 31.7
O 42.1 43.8 43.1 37.9
Fe O 5.3 42.1 1.4 43.8 3.2 43.1 37.9
4.5
Ca Fe 7.1 5.3 5.6 1.4 7.9 3.2 4.5
7.7
Na Ca 9.3 7.1 6.7 5.6 9.0 7.9 14.2
7.7
Na 9.3 6.7 9.0 14.2
There are three distinguishable phases based on the contrast in the backscattered
ThereInare
imaging. thethree distinguishable
pellet, as shown in phases based
the Figure on the contrast
11a; in the backscattered
compositional analysis of areaim-
1aging.
and 3Inarethethe
pellet,
same,as shown
but theincompositional
the Figure 11a;analysis
the compositional analysis
of area 2 shows of area
that it is a1 and
com-3
are the
plex same, of
mixture butcalcium
the compositional analysis
aluminate phase withof area
some2 shows
fractionthat
of itsodium
is a complex
present. mixture
The
of calcium aluminate phase with some fraction of sodium present. The elemental
elemental analysis of point 4 shows that it is a complex mixture of sodium aluminate and analysis
calcium aluminoferrite.
 Brownmillerite (Ca2(Al, Fe)2O5) and srebrodolskite (Ca2Fe2O5) are the iron-containing
phases, which are shown in Figure 11b. These are brighter in the BSD analysis of SEM
image (Figure 11c,d). Calcium titanate (CaTiO3) and calcium ferrite (Ca2Fe2O5) phases con-
trast similarly in the SEM image. Figure 11d shows three main phases in the sintered sam-
Processes 2023, 11, 137 ple. The dark brown phase is the gehlenite (Ca2Al2SiO7) phase, while the calcium
11 of 18 ferrite
(Ca2Fe2O5) and perovskite (CaTiO3) phases look brighter.

(a) (b)
Brownmillerite
\Srebrodolskite

1 4

2
3

(c) (d)
Perovskite
Brownmillerite
Brownmillerite

Perovskite Gehlenite

Figure 11. SEM images of C1.15 A-1150 ◦ C (a–c) and C0.85 A-1150 ◦ C (d), and the identified phases.
Figure 11. SEM images of C1.15A-1150 °C (a–c) and C0.85A-1150 °C (d), and the identified phases.
Brownmillerite (Ca2 (Al, Fe)2 O5 ) and srebrodolskite (Ca2 Fe2 O5 ) are the iron-containing
4. Discussion
phases, which are shown in Figure 11b. These are brighter in the BSD analysis of SEM
image (Figure 11c,d).
4.1. Evolution of PhasesCalcium titanate (CaTiO3 ) and calcium ferrite (Ca2 Fe2 O5 ) phases
contrast similarly in the SEM image. Figure 11d shows three main phases in the sintered
Based on the XRD and SEM analysis results, the major phases found in the sintered
sample. The dark brown phase is the gehlenite (Ca2 Al2 SiO7 ) phase, while the calcium
samples
ferrite (Caare tabulated in Table 7. The melting points found for the stoichiometric phases
2 Fe2 O5 ) and perovskite (CaTiO3 ) phases look brighter.
in the literature are presented. The major phases observed in BR do not exist in the pro-
4. Discussion
duced pellets, and they have been transformed into other compounds via interaction with
4.1. other
the Evolution of Phases of the pellets.
components
Based on the XRD and SEM analysis results, the major phases found in the sintered
samples are tabulated in Table 7. The melting points found for the stoichiometric phases in
the literature are presented. The major phases observed in BR do not exist in the produced
pellets, and they have been transformed into other compounds via interaction with the
other components of the pellets.
Titanium is present in the BR in TiO2 and minor amount in CaTiO3 phase. During
sintering of BR and CaO (that has formed from CaCO3 at lower temperatures) reacts with
TiO2 of BR to form CaTiO3 :
CaO + TiO2 → CaTiO3 (1)
As shown in Figure 12, the standard free energy of CaTiO3 formation decreases
minimally with increasing the sintering temperature.
Gehlenite (Ca2 Al2 SiO7 ) is a major peak in all sintered samples, correlated with both
XRD and SEM analysis. It is a complex phase of calcium aluminosilicate, formed by
two moles of CaO and one mole of Al2 O3 and SiO2 . The standard free energy of gehlenite
formation is relatively lower than other phases, which formed during sintering (Figure 12).
With increasing the sintering temperature, the intensity of gehlenite (Ca2 Al2 SiO7 ) spectra
increases for all different BR and limestone ratio (C0.85 A, C1 A and C1.15 A). As gehlenite is
the dominant phase, its formation is most likely through the interaction of Al2 O3 (from the
decomposed Al hydroxides), SiO2 , and CaO via the following reaction:
 Processes 2023, 11, 137 12 of 18

Processes 2023, 11, x FOR PEER REVIEW 13 of 18

2CaO + Al2 O3 + SiO2 → Ca2 Al2 SiO7 (2)

diffraction and SEM-EDX analysis, it was found that in srebrodolskite small amount of Al
Table 7. The identified phases in the produced pellets at different compositions/temperatures, sorted
is present, which can be the reason for observing the XRD peak is a little bit shifted from
based on their XRD spectrum intensity and SEM image analysis.
the standard peak position. The formation of Ca2Fe2O5 phase may be via Formula (4). Fur-
thermore, ◦the formation of Ca2(Fe,Al)◦2O5 can be via the contribution ofMelting
Al2O3 directly in
Compounds BR C0.85 A-1150 C C1 A-1150 ◦ C C1.15 A-1150 C C1 A-1100 ◦ C C1 A-1200 ◦ C
the reaction or via later mass transport of Al to Ca2Fe2O5 through the dissolution Points of Al2O3
Fe2 O3 into Ca
Major XRD . . 2. Fe2O5 or diffusion
... through . . . solid/semi-solid
... phases in. . .material.1565 C [22]
◦
(hematite)

.2CaO + Fe O . .→
. Ca Fe O
AlOOH
Major XRD ... ... .. ... ...
(4)
(diaspore)
TiO2 (anatase) Major XRD In. . .brownmillerite, . . . there are .two .. atoms of .Ca,
. . five atoms . . .of O and1784
the◦ Csum
[23] of Al and
CaTiO3 Fe atoms
Major is two, such Majorlike Ca2Al 0.365Fe1.63 O5. It
Major was found that
Major Majorthe intensity of brownmil-
Minor XRD 1975 ◦ C [24]
(perovskite) XRD,
lerite (CaSEM XRD,
2Al0.365Fe 1.63O SEM XRD, SEM
5) spectrum decreasesXRD, SEM °C sintering
at 1200 XRD, SEM temperature and maxi-
Ca2 Al2 SiO7
... mum intensity
Major XRD isMajor
found XRDat 1150 °C for
Major XRDa fixed BRXRD
Major and limestone
Major XRD C1A, which
1593 ◦ Cmay
[25] be due to
(gehlenite) and SEM and SEM and SEM and SEM and SEM
more formation of Ca2Al2SiO7 at 1200 °C. The similar trend is found in both C0.85A and
Ca2 (Al,Fe)2 O5
(brownmil- ... C1.15 A. At
Major XRD1200 °C, in Ca
Major XRD2Al0.55Fe 1.44O
Major 5, Al atomic
XRD Majorfraction
XRD increases
Major XRD from 4 to 6.1 at%, which
...
and SEM and SEM and SEM and SEM and SEM
lerite) may be due to high temperature atomic diffusion. The chemical reaction for brownmiller-
Fe2 SiO4
... iteModerate
formation XRD may be written as:
Moderate
Minor XRD Moderate XRD Minor XRD 1204 ◦ C [26]
(fayelite) XRD
CaO Moderate XRD Moderate XRD5 Moderate XRD
1 7 XRD
Moderate
... 6CaO + Fe and
and SEM 2
O SEM
+ Al O + SEM O → 3Minor
Ca in XRD
Fe
and SEM.
Al O ◦ C [27]
. 2572 (5)
(calcium oxide) and SEM 2 and 2
Al6 Ca4 O16 S Moderate Moderate Moderate Moderate
(yellimite)
... Yeelimite
Moderate XRD Ca4O16S) is a XRD
(Al6XRD moderate phase
XRD which found
XRD in all sintered sample. By
...

12CaO.7Al2 O3 the reaction of four moles of CaO, three moles of Al2O3 reacts with one mole◦ of SO3 to form
Minor XRD Minor XRD Minor XRD Minor XRD Minor XRD 1373 C [28]
(mayenite) Al6Ca4O16S. The SO3 comes from the limestone as it was mentioned.
Ca2 Fe2 O5 Minor XRD Minor XRD Minor in XRD Minor in XRD Minor in XRD
1350 ◦ C [29]
(srebrodolskite)
...
and SEM and SEM 4CaO + 3Al O +
and SEM SO
and SEM→ Al Caand
OSEM
S (6)

Figure 12. Standard free energy of formation, 4G◦ (J/mol at 1 atm), for one mole of different phases
Figure 12. Standard free energy of formation, △G° (J/mol at 1 atm), for one mole of different phases
at elevated temperatures. Calculated using Factsage 8.1 software.
at elevated temperatures. Calculated using Factsage 8.1 software.

It is worth mentioning that brownmillerite (Ca2Fe1.63Al0.36O5) and yeelimite

(Al6Ca4O16S) are currently unavailable in Factsage and other thermodynamical database
software and we could not perform the calculations for the formation of these phases.
Processes 2023, 11, 137 13 of 18

There is minor amount of Ca12 Al14 O33 phase found in all sintered samples due to
formation of other oxide complexes such as Ca2 Al2 SiO7 , Ca2 (Fe,Al)2 O5 , Al6 Ca4 O16 S.
Fayelite (Fe2 SiO4 ) is the iron silicate phase, it is a moderate/minor phase in sintered
samples and regarding the existence of hematite and silica in the raw materials its formation
may be shown via the following overall reaction:

1
Fe2 O3 + SiO2 → Fe2 SiO4 + O2 (3)
2
Srebrodolskite (Ca2 Fe2 O5 ) is a minor Fe-containing phase in all sintered samples. The
standard free energy of formation of this phase decreases with sintering temperature rise
as shown in Figure 12. During high temperature sintering, iron oxide in the BR reacts with
CaO to form calcium ferrite (Ca2 Fe2 O5 ) and calcium aluminoferrite (Ca2 (Fe,Al)2 O5 ). The
Calcium ferrite phase is known as Srebrodolskite (Ca2 Fe2 O5 ). However, in X-ray diffraction
and SEM-EDX analysis, it was found that in srebrodolskite small amount of Al is present,
which can be the reason for observing the XRD peak is a little bit shifted from the standard
peak position. The formation of Ca2 Fe2 O5 phase may be via Formula (4). Furthermore, the
formation of Ca2 (Fe,Al)2 O5 can be via the contribution of Al2 O3 directly in the reaction or
via later mass transport of Al to Ca2 Fe2 O5 through the dissolution of Al2 O3 into Ca2 Fe2 O5
or diffusion through solid/semi-solid phases in material.

2CaO + Fe2 O3 → Ca2 Fe2 O5 (4)

In brownmillerite, there are two atoms of Ca, five atoms of O and the sum of Al and Fe
atoms is two, such like Ca2 Al0.365 Fe1.63 O5 . It was found that the intensity of brownmillerite
(Ca2 Al0.365 Fe1.63 O5 ) spectrum decreases at 1200 ◦ C sintering temperature and maximum
intensity is found at 1150 ◦ C for a fixed BR and limestone C1 A, which may be due to more
formation of Ca2 Al2 SiO7 at 1200 ◦ C. The similar trend is found in both C0.85 A and C1.15 A.
At 1200 ◦ C, in Ca2 Al0.55 Fe1.44 O5 , Al atomic fraction increases from 4 to 6.1 at%, which may
be due to high temperature atomic diffusion. The chemical reaction for brownmillerite
formation may be written as:

5 1 7
6CaO + Fe2 O3 + Al2 O3 + O2 → 3(Ca2 Fe1.63 Al0.36 O5 ) (5)
2 2 2
Yeelimite (Al6 Ca4 O16 S) is a moderate phase which found in all sintered sample. By
the reaction of four moles of CaO, three moles of Al2 O3 reacts with one mole of SO3 to form
Al6 Ca4 O16 S. The SO3 comes from the limestone as it was mentioned.

4CaO + 3Al2 O3 + SO3 → Al6 Ca4 O16 S (6)

It is worth mentioning that brownmillerite (Ca2 Fe1.63 Al0.36 O5 ) and yeelimite (Al6 Ca4 O16 S)
are currently unavailable in Factsage and other thermodynamical database software and
we could not perform the calculations for the formation of these phases.
The observed compounds’ melting points in Table 7 are higher than the applied sin-
tering temperatures in the sintered pellets. Partial melting or softening of compounds
normally starts at around 0.6–0.8 Tm , near the sintering temperature of 1200 ◦ C for com-
pounds such as Fe2 O3 , Ca2 Fe2 O5 , Ca2 Al2 SiO7 , and TiO2 . On the other hand, the presented
melting points in Table 2 are for the stoichiometric (pure) compounds, while the pel-
lets are not pure and contain impurities; therefore, they have real melting points lower
than those in Table 7. Hence, at the applied sintering temperatures, the reactants in
Formula (1) to (6) could interact properly within the applied two hours of sintering to yield
the products and the formation of the same phases at 1100–1200 ◦ C. The existence of the
not significant number of reactants (Al2 O3 , Fe2 O3 , CaO, TiO2 , SiO2 ) indicates that they
have been consumed completely via the chemical Formula (1) to (6).
Processes 2023, 11, 137 14 of 18

In the sintered pellet samples the major fraction of iron and alumina present in brown-
millerite (Ca2 Fe1.63 Al 0.36 O5 ) in addition to iron present in srebrodolskite (Ca2 Fe2 O5 ), and
fayalite (Fe2 SiO4 ), while alumina is present in gehlenite (Ca2 Al2 SiO7 ). After reduction with
hydrogen, most of the brownmillerite is converted to metallic iron and mayenite, which
was described in our previous work [30]. Alumina can be separated by sodium carbonate
leaching of mayenite, and leach residue goes for magnetic separation of iron recovery.
Some amount of alumina lost in gehlenite as gehlenite is not leachable phase. In the main
approach in the Harare Project, however, Fe separation from the reduced pellets is be
performed by magnetic separation and then the alumina recovery from the non-magnetic
portion comes via alkaline leaching.

4.2. Physical Properties of Pellets

The higher amount of added calcite causes higher porosity in the pellets. When the
sample temperature increases, CaCO3 decomposes to CaO and CO2 , and the decomposi-
tion temperature is in range of 700–800 ◦ C has been reported [31], while the theoretical
decomposition temperature is 887 ◦ C as per HSC version 9.9.2.3. Therefore, the higher
weight loss of the samples in sintering when more limestone added is due to the greater
CO2 release from the samples.
The mass loss due to calcite decomposition is calculated as 16%, 17%, and 18% for
pellets C0.85 A, C1 A, and C1.15 A, respectively. However, the LOI for the C1 A-1150 ◦ C is
around 22%, so there is 5% difference in the weight loss between calcite decomposition
and LOI. It is worth noting that the calcite decomposition weight difference is almost
the same at different sintering temperatures for a fixed composition. The 5% weight loss
difference between the calcite decomposition and loss of ignition (LOI) may be due to
diaspore, gibbsite, and goethite decomposition. Thermal decomposition of the major phase
diaspore is between 530 ◦ C to 650 ◦ C [32]. There may be some chemisorbed water that
causes weight loss during sintering.
At higher sintering temperatures, the observed slightly higher weight loss is related to
some low vapor pressure compounds in BR and limestone, which may vaporize during sin-
tering. XRF results in Table 5 show that the weight percentage of all oxides increases when
dry pellets are sintered at 1150 ◦ C except Na2 O, indicating a little more weight loss of Na2 O
during sintering at higher temperatures. There are two compounds of alkali metal oxides
that formed after sintering, namely jadeite (AlNaO6 Si) and katoite (Al2.1 Fe1.9 K0.9 O12 Si2.8 ).
Actually, on the surface of solid particles in BR there is NaOH, which originates from
the Bayer process, and yields Na2 O in the later sintering process. During sintering, the
NaOH on BR particles react with Al2 O3 and SiO2 in BR and yields jadeite, which provides
strength to the sintered pellets [33]. However, these compounds are present in a very
small fraction. These compounds have hardening behaviors, but it was difficult to observe
the notable effect of Na2 O in the experiments due to its minuscule amount compared to
CaO. At high sintering temperature, 1200 ◦ C and above some compounds become softened
or semi-molten, usually at 0.6–0.8 Tm of these compounds (Table 7). Therefore, more
fusion/sintering occurs, and it causes increase of pellet strength; however, it reduces the
porosity of the pellets. As Na2 O’s melting point is low (1132 ◦ C) it becomes molten at
higher applied temperature and interacts with adjacent oxides (Al2 O3 and SiO2 ) and forms
jadeite, as we observed in XRD. The formation of molten Na2 O is important because it
helps form primary liquid phase and accelerates the migration and recrystallization of
solids, a mechanism that may propose is the dissolution of Al2 O3 and SiO2 into molten
Na2 O and the formation of jadeite during the sintering step via mass transport between
solid and liquid and even solid to solid regarding the high melting point jadeite (above
1500 ◦ C). This complex oxide formation between the pellets’ particles increases the strength.
BET surface area and porosity of the pellets are largely related to each other, as
observed in Table 2. It was found that the porosity of the pellets increases with an increase
in limestone addition; however, it decreases with increasing temperature. From the SEM
images (Figure 8) we observe significant porosity loss via sintering at 1200 ◦ C compared
 BET surface area and porosity of the pellets are largely related to each other
served in Table 2. It was found that the porosity of the pellets increases with an i
in limestone addition; however, it decreases with increasing temperature. From th
images (Figure 8) we observe significant porosity loss via sintering at 1200 °C com
Processes 2023, 11, 137 to the lower temperatures as most of the particles being sintered. Comparing 15 of 18 m
porosimetry and BET surface area, the latter may be more accurate because in B
used nitrogen adsorption isotherm, and as nitrogen has a smaller atomic size, it c
to themore
fuse lowerintotemperatures as most
micropores, of the
which isparticles being sintered.
not possible Comparing
by pressurized mercury
mercury porosim
porosimetry and BET surface area, the latter may be more accurate because in BET, we used
It is found that the CO2 releases from pellets and porosity evolution for the s
nitrogen adsorption isotherm, and as nitrogen has a smaller atomic size, it can diffuse more
show similar trends
into micropores, atnot
which is constant
possiblesintering temperatures
by pressurized for different BR and limest
mercury porosimetry.
tios as
It isshown
found thatin Figure
the CO2 13. As the
releases fromlimestone
pellets and amount increases,
porosity evolution for more CO2 leaves
the samples
show similar trends at constant sintering temperatures for different
sample during sintering, resulting in higher porosity. Hence, we may conclude t BR and limestone
ratios as shown in Figure 13. As the limestone amount increases, more CO2 leaves out the
rosity evolution correlates with the amount of limestone used and further calcite
sample during sintering, resulting in higher porosity. Hence, we may conclude that porosity
position. Therefore,
evolution correlates withitthe
is amount
expected that if quicklime
of limestone (CaO)calcite
used and further is used, the porosity is
decomposition.
pendent
Therefore,on it isCaO addition
expected that if compared to CaCO
quicklime (CaO) 3 addition.
is used, the porosity is less dependent on
CaO addition compared to CaCO3 addition.

◦
13.Released
Figure 13.
Figure CO2CO
Released gas2 and
gasmeasured porosityporosity
and measured for pellets for
withpellets
composition
with (Cx A) at 1150 C(CxA) at
composition
sintering temperature.
sintering temperature.
4.3. Mechanical Properties of Pellets
4.3. Mechanical Properties
We found that of Pellets
during sintering, the outer surface of the pellets became semi-molten or
achieved partial fusion at 1200 ◦ C, causing them to stick to each other. For these pellets,
We found that during sintering, the outer surface of the pellets became semi-
the tumbler index and abrasion index, and breaking load of the pellets were the best.
or achieved
Obviously, thepartial
slag-kindfusion at 1200 °C,
phase formation causing
during them
sintering to stick to each
is accompanied by theother. For these
formation
the tumbler
of stronger indexbetween
bonding and abrasion index,
the pellet andMoreover,
particles. breaking theload of the pellets
mechanical propertieswere
of the be
viously, the slag-kind
pellets depend phase
on the porosity, andformation
lower porosityduring sintering
is directly relatedistoaccompanied
the lower abrasionby the for
index. As SEM results indicated, the pellets sintered at 1100 ◦ C did not have many fusion
of stronger bonding between the pellet particles. Moreover, the mechanical prope
and semi-molten phases.
pellets depend on the porosity, and lower porosity is directly related to the lower a
Figure 14a shows that when the porosity increases the breaking load decreases regard-
index. As SEM results
ing the composition indicated,
of pellets. the pellets
As mentioned above,sintered
porosityat 1100 °C
depends ondid not have many
the sintering
and semi-molten
temperature and thephases.
amount of limestone added. More limestone addition causes higher
porosity, which14a
Figure decreases
shows thethat
strength
whenof pellets. Figure 14b
the porosity indicates that
increases thethe pellet strength
breaking load decrea
increases for a fixed composition with increasing sintering temperature, but the porosity
garding the composition of pellets. As mentioned above, porosity depends on the
decreases. This is due to the formation of stronger pellets via more sintering and in parallel
ing temperature
porosity and the
loss. In principle, amount
ceramics of limestone
with higher porosity and added. More limestone
lower sintering are weaker inaddition
higher porosity,
mechanical which
properties, whichdecreases thefor
is seen here strength ofsintered
the pellets pellets.atFigure 14b indicates that th
lower temperatures.
 strength increases for a fixed composition with increasing sintering temperature, but the
porosity decreases. This is due to the formation of stronger pellets via more sintering and
in parallel porosity loss. In principle, ceramics with higher porosity and lower sintering
Processes 2023, 11, 137 16 of 18
are weaker in mechanical properties, which is seen here for the pellets sintered at lower
temperatures.

Figure 14. Porosity vs. breaking load of different compositions at fixed sintering temperature 1150
Figure 14. Porosity vs. breaking load of different compositions at fixed sintering temperature
°C (a), and at different temperatures for fixed composition C1A (b).
1150 ◦ C (a), and at different temperatures for fixed composition C1 A (b).
5.
5. Conclusions
Conclusions
Experimental
Experimental work workon onthe thepelletizing
pelletizing of of
bauxite
bauxite residue
residueandand limestone
limestoneand high
and tem-
high
perature sintering was carried out. The effect of lime addition
temperature sintering was carried out. The effect of lime addition and sintering temperature and sintering temperature
were studied.
were studied. The main main conclusions
conclusions are are summarized
summarized as: as:
1.
1. Pellet
Pellet density and weight loss are increased withhigher
density and weight loss are increased with highersintering
sinteringtemperature
temperature appli-
appli-
cation, which is partly explained by the decrease
cation, which is partly explained by the decrease in BET surface area in BET surface area andandporosity;
poros-
on
ity;the
onother hand,hand,
the other BET surface area and
BET surface areaporosity
and porosityare increased with more
are increased withCaCOmore3
addition.
CaCO3 addition.
2.
2. It
It was
was found
found that that inin view
view of of porosity
porosity and pellet strength,
and pellet strength, sintering
sintering temperature
temperature of of
1150
1150 C yields acceptable pellets with about 90% tumbler index and 55% porosity.
°C
◦ yields acceptable pellets with about 90% tumbler index and 55% porosity.
3.
3. Tumble
Tumble and and abrasion
abrasionindexes
indexesare arebetter
betterforfor thethe pellets
pellets sintered
sintered at higher
at higher tempera-
temperatures
tures in range of 1100
◦ °C to 1200
◦ °C and
in range of 1100 C to 1200 C and the less CaCO3 added pellets.the less CaCO 3 added pellets.
4.
4. There
There is is inverse
inverse correlation
correlation betweenbetween the the strength
strength of of the
the pellets
pellets andand thethe porosity,
porosity, with
with
porosity
porositydecreases
decreasesthe thestrength
strength of of
pellets
pellets is increased,
is increased, for both
for bothvarying sintering
varying tem-
sintering
perature
temperature in range
in rangeof 1100
of 1100°C to◦ C1200 °C and
to 1200 ◦ C composition
and composition of pellets.
of pellets.
5. Iron
Iron present in the sintered pellets mainly in three different phases
present in the sintered pellets mainly in three different phases suchsuch as as brown-
brown-
millerite
millerite (Ca (Fe,Al) O ), srebrodolskite
2 (Fe,Al)2 O5 ), srebrodolskite
2 2 5 (Ca 2 Fe O ), and
2 Fe2 O5 ), and
2 5 fayalite (Fe
(Fe22SiO 4 ). Among
4 ).
these
these brownmillerite
brownmillerite (Ca (Ca22(Fe,Al)
(Fe,Al)22OO5)5 )isisthe
themajor
majoriron ironcontaining
containingphase. phase.
6. TheThe AlAl fraction
fraction in in the
the Ca
Ca22(Fe,Al)
(Fe,Al)22OO55increases
increaseswith withincreases
increasesin inthe
thesintering
sinteringtemper-
temper-
ature
ature inin range
range of of 1100
1100 °C ◦ C to to 1200 ◦ C, which
1200 °C, which may may be be duedue to more mass transport in
sintering
sintering via via high
high temperature
temperature diffusion.
diffusion.
7. Gehlenite,
Gehlenite, brownmillerite,
brownmillerite, and and perovskite
perovskite are are the
the major
major spectrums
spectrums in the sintered
pelletsand
pellets andgehlenite
gehlenitespectrum
spectrum becomes
becomes moremore intense
intense withwith increases
increases in sintering
in sintering tem-
temperature
perature °C to◦ C
(1100(1100 to 1200
1200 °C). ◦ C).

Author Contributions:
Author Contributions: Conceptualization,
Conceptualization, M.K.K.
M.K.K. and
and J.S.;
J.S.; methodology,
methodology, M.K.K.
M.K.K. and
and J.S.;
J.S.; software,
software,
M.K.K.
M.K.K. and
and J.S.;
J.S.; validation,
validation, M.K.K.
M.K.K. and
and J.S.;
J.S.; formal
formal analysis,
analysis, M.K.K.
M.K.K. and
and J.S.;
J.S.; investigation,
investigation, M.K.K.;
M.K.K.;
resources,
resources, J.S.;
J.S.; data
data curation,
curation, M.K.K.;
M.K.K.; writing—original
writing—original draftdraft preparation,
preparation, M.K.K.;
M.K.K.; writing—review
writing—review
and
and editing,
editing, M.K.K.
M.K.K. andand J.S.;
J.S.; visualization,
visualization, M.K.K.
M.K.K. and
and J.S.;
J.S.; supervision,
supervision, J.S.;
J.S.; project
project administration,
administration,
M.K.K.
M.K.K. and J.S.; funding acquisition, J.S. All authors have read and agreed to the
and J.S.; funding acquisition, J.S. All authors have read and agreed to the published
published version
version
of
of the
the manuscript.
manuscript.
Funding:
Funding: This
This project
project has
has received
received funding
funding from
from the
the European
European Union’s
Union’s Horizon
Horizon 2020
2020 research
research and
and
innovation
innovation program under grant
program under grant agreement
agreement 958307.
958307.

Data Availability Statement: Not applicable.

Processes 2023, 11, 137 17 of 18

Acknowledgments: This project has received funding from the European Union’s Horizon 2020
research and innovation program under grant agreement No. 958307. This publication represents
only the authors’ views, exempting the Community from any liability. The Harare Project website is
https://h2020harare.eu/ (accessed on 22 November 2022).
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Balomenos, E.; Panias, D.; Paspaliaris, I. Energy and Exergy Analysis of the Primary Aluminum Production Processes: A Review
on Current and Future Sustainability. Miner. Process. Extr. Metall. Rev. 2011, 32, 69–89. [CrossRef]
2. Borra, C.R.; Blanpain, B.; Pontikes, Y.; Binnemans, K.; Van Gerven, T. Recovery of Rare Earths and Other Valuable Metals from
Bauxite Residue (Red Mud): A Review. J. Sustain. Metall. 2016, 2, 365–386. [CrossRef]
3. Evans, K. The History, Challenges, and New Developments in the Management and Use of Bauxite Residue. J. Sustain. Metall.
2016, 2, 316–331. [CrossRef]
4. Safarian, J.; Kolbeinsen, L. Sustainability in Alumina Production from Bauxite. Sustain. Ind. Process. Summit 2016, 5, 75–82.
5. Kumar, S.; Kumar, R.; Bandopadhyay, A. Innovative Methodologies for the Utilisation of Wastes from Metallurgical and Allied
Industries. Resour. Conserv. Recycl. 2006, 48, 301–314. [CrossRef]
6. Wang, M.; Liu, X. Applications of Red Mud as an Environmental Remediation Material: A Review. J. Hazard. Mater. 2021,
408, 124420. [CrossRef]
7. Lyu, F.; Hu, Y.; Wang, L.; Sun, W. Dealkalization Processes of Bauxite Residue: A Comprehensive Review. J. Hazard. Mater. 2021,
403, 123671. [CrossRef]
8. Power, G.; Gräfe, M.; Klauber, C. Bauxite Residue Issues: I. Current Management, Disposal and Storage Practices. Hydrometallurgy
2011, 108, 33–45. [CrossRef]
9. Cardenia, C.; Xakalashe, B.; Balomenos, E.; Panias, D.; Friedrich, B. Reductive roasting process for the recovery of iron oxides
from bauxite residue through rotary kiln furnace and magnetic separation. In Proceedings of the 35th International ICSOBA
Conference, Hamburg, Germany, 2–5 October 2017; pp. 2–5.
10. Yin, P.T.; Buhle Xakalashe, B.F.; Panias, D.; Vassiliadou, V. Carbothermic reduction of bauxite residue for iron recovery and
subsequent aluminium recovery from slag leaching. In Proceedings of the 35th International ICSOBA Conference, Hamburg,
Germany, 2–5 October 2017; pp. 603–613.
11. Archambo, M.S.; Kawatra, S.K. Utilization of Bauxite Residue: Recovering Iron Values Using the Iron Nugget Process.
Miner. Process. Extr. Metall. Rev. 2021, 42, 222–230. [CrossRef]
12. Lazou, A.; Van Der Eijk, C.; Tang, K.; Balomenos, E.; Kolbeinsen, L.; Safarian, J. The Utilization of Bauxite Residue with
a Calcite-Rich Bauxite Ore in the Pedersen Process for Iron and Alumina Extraction. Metall. Mater. Trans. B 2021, 52, 1255–1266.
[CrossRef]
13. Lazou, A.; Van der Eijk, C.; Balomenos, E.; Safarian, J. Smelting Reduction of Bauxite Residue and Beneficiation By-Product
in View of a Leachable Slag and Pig Iron Production. In Proceedings of the European Metallurgical Conference, Düsseldorf,
Germany, 23–26 June 2019; pp. 17–34.
14. Gräfe, M.; Power, G.; Klauber, C. Bauxite Residue Issues: III. Alkalinity and Associated Chemistry. Hydrometallurgy 2011,
108, 60–79. [CrossRef]
15. Wagner, G.H. Making Concrete Articles and the Like; 1932. Available online: https://patents.google.com/patent/US1865732A/en
(accessed on 22 November 2022).
16. Jaquays, C. Building and Other Materials Containing Treated Bauxite Tailings and Process for Making Same. U.S. Patent
20050087107, 28 April 2005.
17. Azof, F.I.; Yang, Y.; Panias, D.; Kolbeinsen, L.; Safarian, J. Leaching Characteristics and Mechanism of the Synthetic Calcium-
Aluminate Slags for Alumina Recovery. Hydrometallurgy 2019, 185, 273–290. [CrossRef]
18. Blake, H.E. Adaptation of the Pedersen Process to the Ferruginous Bauxites of the Pacific Northwest; U.S. Department of the Interior,
Bureau of Mines: Washington, DC, USA, 1967; p. 6939.
19. Azof, F.I.; Safarian, J.; Kolbeinsen, L. The leachability of calcium aluminate phases in slags for the extraction of alumina. In
Proceedings of the 35th International ICSOBA Conference, Hamburg, Germany, 2–5 October 2017.
20. ISO 3271; Iron Ores for Blast Furnace and Direct Reduction Feedstocks–Determination of the Tumble and Abrasion Indices. ISO:
Geneva, Switzerland, 1995.
21. Monsen, B.E.; Thomassen, E.S.; Bragstad, I.; Ringdalen, E.; Hoegaas, P.H. Characterization of DR pellets for DRI applications. In
Proceedings of the Association for Iron and Steel Technology Conference Proceedings, Cleveland, OH, USA, 4–7 May 2015.
22. Qu, Y.; Yang, Y.; Zou, Z.; Zeilstra, C.; Meijer, K.; Boom, R. Melting and Reduction Behaviour of Individual Fine Hematite Ore
Particles. ISIJ Int. 2015, 55, 149–157. [CrossRef]
23. Li, Y.; Ishigaki, T. Thermodynamic Analysis of Nucleation of Anatase and Rutile from TiO2 Melt. J. Cryst. Growth 2002,
242, 511–516. [CrossRef]
Processes 2023, 11, 137 18 of 18

24. Poirier, J. 1P Lindemann Law and the Melting Temperature of Perovskites. Phys. Earth Planet. Inter. 1989, 54, 364–369. [CrossRef]
25. Charlu, T.V.; Newton, R.C.; Kleppa, O.J. Thermochemistry of Synthetic Ca2 Al2 SiO7 (Gehlenite)-Ca2 MgSi2 O7 (Åkermanite)
Melilites. Geochim. Cosmochim. Acta 1981, 45, 1609–1617. [CrossRef]
26. Jackson, W.E.; De Leon, J.M.; Brown, G.E., Jr.; Waychunas, G.A.; Conradson, S.D.; Combes, J.-M. High-Temperature XAS Study of
Fe2 SiO4 Liquid: Reduced Coordination of Ferrous Iron. Science 1993, 262, 229–233. [CrossRef]
27. Luna Vera, F.; Guancha Chalapud, M.; Castillo Viveros, I.; Vásquez Medina, E.A. From Eggshells to Quicklime: Using Carbonate
Cycle as an Integrating Concept to Introduce Students to Materials Analysis by TGA and FTIR. J. Chem. Educ. 2018, 95, 625–630.
[CrossRef]
28. Tolkacheva, A.S.; Shkerin, S.N.; Korzun, I.V.; Plaksin, S.V.; Khrustov, V.R.; Ordinartsev, D.P. Phase Transition in Mayenite
Ca12 Al14 O33 . Russ. J. Inorg. Chem. 2012, 57, 1014–1018. [CrossRef]
29. Ceretti, M.; Corallini, S.; Paulus, W. Influence of Phase Transformations on Crystal Growth of Stoichiometric Brownmillerite
Oxides: Sr2 ScGaO5 and Ca2 Fe2 O5 . Crystals 2016, 6, 146. [CrossRef]
30. Kar, M.K.; Van Der Eijk, C.; Safarian, J. Hydrogen reduction of high temperature sintered and self-hardened pellets of bauxite
residue produced via the addition of limestone and quicklime. In Proceedings of the 40th International ICSOBA Conference,
Athens, Greece, 10–14 October 2022; p. 11.
31. Karunadasa, K.S.P.; Manoratne, C.H.; Pitawala, H.; Rajapakse, R.M.G. Thermal Decomposition of Calcium Carbonate (Calcite
Polymorph) as Examined by in-Situ High-Temperature X-Ray Powder Diffraction. J. Phys. Chem. Solids 2019, 134, 21–28.
[CrossRef]
32. Kloprogge, J.T.; Ruan, H.D.; Frost, R.L. Thermal Decomposition of Bauxite Minerals: Infrared Emission Spectroscopy of Gibbsite,
Boehmite and Diaspore. J. Mater. Sci. 2002, 37, 1121–1129. [CrossRef]
33. Jamil, N.H.; Abdullah, M.M.A.B.; Ibrahim, W.M.A.W.; Rahim, R.; Sandu, A.V.; Vizureanu, P.; Castro-Gomes, J.;
Gómez-Soberón, J.M. Effect of Sintering Parameters on Microstructural Evolution of Low Sintered Geopolymer Based
on Kaolin and Ground-Granulated Blast-Furnace Slag. Crystals 2022, 12, 1553. [CrossRef]

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual
author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to
people or property resulting from any ideas, methods, instructions or products referred to in the content.