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Iron Ore Sintering: Process: Article
Iron Ore Sintering: Process: Article
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MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW
2017, VOL. 38, NO. 4, 215–227
http://dx.doi.org/10.1080/08827508.2017.1288115
ABSTRACT KEYWORDS
Sintering is a thermal agglomeration process that is applied to a mixture of iron ore fines, recycled Agglomeration; CAP process;
ironmaking products, fluxes, slag-forming agents, and solid fuel (coke). The purpose of the sintering flame front; HPS process;
process is manufacturing a product with the suitable characteristics (thermal, mechanical, physical and iron ore; MEBIOS process;
sintering; softening and
chemical) to be fed to the blast furnace. The process has been widely studied and researched in the iron
melting
and steelmaking industry to know the best parameters that allow one to obtain the best sinter quality.
The present article reviews the sintering process that the mixture follows, once granulated, when it is
loaded onto the sinter strand. There, the sinter mixture is partially melted at a temperature between
1300-1480°C and undergoes a series of reactions that forms the sinter cake to be loaded into the blast
furnace to produce pig iron.
CONTACT D. Fernández-González fernandezgdaniel@uniovi.es Department of Materials Science and Metallurgical Engineering, School of Mines, Energy and
Materials, University of Oviedo, Oviedo, Asturias 33004, Spain.
© 2017 Taylor & Francis Group, LLC
216 D. FERNÁNDEZ-GONZÁLEZ ET AL.
sintering process. Secondly, and over the first layer, a second sidered other granulometric fractions: 10 and 20 mm
layer of fine material (0-8 mm) is charged. This second layer is (Umadevi et al., 2011; Ying et al. 2011) or 10 and 15 mm
formed by fine mineral, return fines, fluxes and coke. (Gupta 2010).
Then, the pallet car passes bellow an initializing furnace, ● More than 20 mm (Umadevi et al., 2011) o more than
where the combustible ignition takes place in the surface of 15 mm (Gupta 2010) are directly sent to the blast fur-
the mix. At the same time, the mix is subjected to down- nace. Maximum grain sizes <50 mm according to Lu
draught suction through the load. and Ishiyama 2015.
The pallet car continues the process and the combustion
progresses in the direction of the gas flow. In this way, the
Return fines are unavoidably formed during the sintering
sintering process takes place. The combustion process does
process, and are recycled back into the sintering process, mak-
not happen simultaneously in the whole thickness of the bed.
ing up 30 to 40% of the iron bearing materials. Wu et al. 2013,
On the contrary, combustion happens as a horizontal layer
studied the proper ratio of using return fines in the sintering
that moves vertically through the bed. The thickness of this
process. They observed that return fines from sintering sieving
layer is a small fraction of the bed. Permeability is a quality
were a little easily assimilated than that from the blast furnace
requirement for the load, and for that reason the granulation
sieving due to the lower high-Ca calcium ferrite content (Wu
process is previously used (permeability is improved during
et al. 2013). Wu et al. 2013 suggested an optimal ratio of 30 mass
granulation) (Fernandez-González et al., 2017). In the region
% (max.) return fines from blast furnace sieving and 20 mass %
above the combustion zone, very hot sintered product heats
return fines from sintering sieving.
the air that passes through this layer. In this way, pre-heated
Four zones can be identified in the bed height:
air arrives to the combustion area. The heat of the air/gases
previously heated is absorbed in these cold sections, causing
preheating of the load and evaporation of the water. In this ● Cold and wet zone: Includes the zone of the sinter bed
context, high temperatures that cause partial melting are with a temperature lower than 100°C. This area is
reached, and the sintering process takes place. formed by the mix to be sintered, with upper limit
This high thermal efficiency is caused by heat accumula- saturated in water/water vapor.
tion in a partial layer of the load called sintering zone or ● Drying zone: Sinter area with temperatures between
flame front. The flame front progresses at 10-30 mm/min 100°C and 500°C. The vaporization of the mix moisture
(23.9-27.7 mm/min, Zhou et al., 2015; 12-28 mm/min, and subsequent dehydration of hydroxides take place.
Loo and Dukino 2014) towards the sintering grate. In a ● Reaction zone (maximum temperatures: 1300-1480°C,
bed height of 500-600 mm the process would take 25 min- according to Eisele and Kawatra, 2003): Includes the
utes (Gosh and Chaterjee, 2008). zone of the sinter bed with a temperature between
Once the end of the strand is reached, the sintered material 500°C (coke ignition beginning) and 900°C (cooling
is discharged and subjected to cooling, crushing, and screen- period beginning). The main processes that happen in
ing. Obtained product can be divided into three granulo- this zone are: coke combustion (exothermal), carbonates
metric fractions: decomposition (endothermal), solid phase reactions,
reduction and re-oxidation of iron oxides and reactions
● Between 0 and 5 mm (0 and 10 mm, according to Gupta of formation of the sintered mass.
2010), called return fines, which are sent to the feeding ● Cooling zone: This zone is found immediately after the
hoppers (Williams 1983; Lu and Ishiyama 2015; Loo and reaction zone. Cooling and re-crystallization of the sin-
Dukino 2014; Mochón 2014a). tered product take place. There is a superficial zone
● Sinter with a granulometry within 5 and 20 mm is used where the sinter layer is brittle than in the rest of the
as hearth layer in the sinter strand. Other authors con- sinter bed.
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 217
Nozawa et al. 2013 investigated the cause of sinter process Kawaguchi and Hara, 2013 observed a good productivity and
fluctuations to enable lowered consumption of carbon, thus exhaust gas (NOX, SOX, dust, dioxins) when using biomass
lowering carbon dioxide emissions. Frequency analysis of carbonized char as carbon material, but operation is necessary
plant data (exhaust gas temperature at one wind-box, mixture to be optimized (size and moisture control of biomass char) as
charging level and mixture moisture content) indicated that a consequence of the high biomass char combustion rate.
feed mixture moisture variations were linked to fluctuations Sinter yield is similar to the obtained with anthracite and
of gas exhaust temperature at the particular wind-box. Process coke when biomass char is used, and it was observed the
control was improved by controlling the feed mixture moist- effectiveness of biomass char to decrease CO2, NOX, SOX,
ure content in a narrow band of values, thus enabling lower dust, etc. emission in sinter exhaust gas.
carbon consumption and fewer carbon dioxide emissions. Lu et al., 2013 studied the substitution charcoal as an
alternative fuel for coke breeze. They observed that compared
with coke breeze, sinter mixtures containing charcoal required
2.1. Combustibles for the sintering process
higher mix moisture contents to achieve optimum granula-
Cokes and anthracites are used in general as solid fuels in the tion. Lu et al., 2013 observed that fuel rate increased consid-
iron ore sintering process, but they must be reconsidered due erably with charcoal substitution because of the increased fuel
to the rise of coke price, the unstable supply of anthracites and addition and decreased sinter yield (this question did not
the global warming by CO2 emissions (Murakami et al., 2013). imply a reduction of sinter productivity, on the contrary,
Arikata et al., 2013 studied the reduction of specific coke sintering speed and productivity increased with increases in
breeze consumption by examination of the influence that charcoal substitution rate). Lu et al., 2013 observed that with
coke breeze morphology and pseudo-particles structure have increasing substitution of charcoal for coke breeze implied
on sintering quality. They controlled the coke breeze mor- that both CO and CO2 concentrations in the waste gas
phology in pseudo-particles by delaying the timing of coke increased, and that both SO2 and NOX decreased.
breeze addition in the granulation process. As a consequence Zhang et al., 2014, studied the effect of CO and CO2 in
of adding more coke breeze in the later stage of granulation it suction gas and they observed that the presence of a small
was observed that permeability improved, but also much of amount of CO was beneficial to improve the coke combustion
coke breeze stayed in the surface layer of pseudo particles or efficiency, but also sinter productivity, yield and sinter
in free particle leading to improve quality and burn through strength. Zhang et al., 2014 also observed that excessive
speed (BTS). Arikata et al., 2013 observed that when the entire amount of CO2 impair coke combustion efficiency and sinter-
charge of coke breeze was added in the latter stage, combus- ing indexes. Zhang et al., 2014 suggested that CO2 content in
tion quality was improved, but conduction and accumulation suction gas should be lower than 5 vol. %.
of heat impaired, reducing yield as a consequence of heat loss. Fujino et al., 2013 studied the effect of adding metallic Fe
Arikata et al., 2013 searched for a ratio of the second-stage particles (as an alternative agglomeration agent) to coke with
addition (after moisture addition). With a ratio of 50%, sinter the purpose of reducing CO2 emissions in the sintering pro-
quality and permeability were improved, while maintaining cess. Fujino et al., 2013 observed changes in the pressure of
good BTS, because the area of the sintering bed with tem- the sinter bed, which caused a decrease in permeability
perature at 1200°C or higher was expanded, enabling the (consequence of the blockage that produces the increasing
reduction of coke breeze consumption. amount of formed melt).
Fan et al., 2014, studied the use of straw char as a Ohno et al., 2013 studied the combustion rate in the fine
supplementary fuel for coke in iron ore sintering. They layer of the quasi-particle, considering void ratio and liquid
studied two possible types of carbonization: one-stage car- formation. They observed that coke combustion rate
bonization (700°C, 10-25°C/min, carbonization time of 30 decreased with the increasing of liquid formation as liquid
min) and two-stage carbonization (stage-1: 500°C, stage-2: phase in quasi-particle prevented oxygen diffusion. Ohno
700°C); having similar volatile and fixed carbon contents et al., 2013 also observed that the higher mixing ratio of
than coke breeze. Fan et al., 2014, concluded that straw coke, the larger effective diffusion coefficient of oxygen as a
char prepared as mentioned is able to replace coke breeze consequence of that mixing ratio of coke made higher the
by 20% (one-stage carbonization) and 40% (two-stage car- void ratio in the sample after coke combustion.
bonization), with emission reduction for SOX and for NOX,
10.98% and 38.15% (one-stage carbonization) and 12.67%
and 22.53% (two-stage carbonization), respectively. 3. Alternative processes to sintering and pelletizing
Fan et al., 2015 developed a coke-biochar composite from
3.1. HPS process: Hybrid Pelletized Sinter
coking coal and raw straw, and they used it as fuel for the
sintering process. They concluded that small changes in sinter The HPS process is based on the incorporation of conven-
quality are achieved for 40-60% of coke-biochar composite tional processes for the production of both sinter and pellets.
replacement. The fuel nitrogen conversion rate is decreased This process was developed by the NKK (Nippon Kokan
by 8.3% during combustion. Keihin, now JFE Steel Corporation) with the purpose of
Kawaguchi and Hara, 2013 suggested the utilization of using large amounts of fine iron ores, including pellet feed
biomass (raw-biomass and biomass carbonized char) for with high iron content. As opposed to the traditional sintering
iron ore sintering. They observed that yield and exhaust gas process, the blended ore, limestone and burned lime are firstly
were not good when using raw biomass as carbon material. mixed and pelletized in the Hybrid Pelletized Sinter
218 D. FERNÁNDEZ-GONZÁLEZ ET AL.
equipment. This process used disk pelletizers to produce and coarsely granulated material), while the induction bed
green pellets that are coated with coke breeze before being consisted of pisolitic limonite ore blended with coke and
charged onto the sinter machine. A commercial plant using CaO. The aim of the MEBIOS process is the formation of a
HPS process with an annual capacity of 6 million tons per ventilation route in the sintering bed by creating a low-density
annum was built by the JFE Steel Corporation at Fukuyama area around the large pellets arising from a kind of wall effect
(Lu and Ishiyama 2015). and suppression of sinter bed shrinkage due to support of the
load by dense large pellets in the upper part of the sinter bed
(Lu and Ishiyama 2015).
3.2. MEBIOS: Mosaic Embedding Iron Ore Sintering Another version of this process is RF-MEBIOS
The behavior of raw mixes with high goethite ore content in (return fine-mosaic embedding iron ore sintering) that was
sinter bed structure and permeability have been being studied developed to utilize return fines as the dry particles
since 1980’s by Japanese steel mills (Otomo et al. 1996; Yang (Yamaguchi et al., 2013; Matsumura et al., 2013). Small dry
et al. 2000). The basic mineralogy of West Angelas iron ore particles charged into the packed sinter bed have a similar
(Australia) is an association of martite and goethite. Marra effect on controlling the bed structure due to friction
Mamba (Australia) ores present a wide range of lithological between the dry and wet particles. The utilization of return
and mineral types from hard/dense to soft/highly porous and fines as the dry particles eliminates the requirements for
from martite to goethite and ochreus goethite. In this way, the drying coarse ore particles. The productivity is increased at
softest ores can produce a high proportion of ultrafine parti- the same charging moisture content in the sinter mixture as
cles (up to 30% <0.15 mm). In 2001 ISIJ began a research a consequence of the higher permeability of the packed bed
project on porous meso-mosaic texture sinter with the pur- (due to the increase in the pseudo-particle size during gran-
pose of improving sintering in the case of incorporating ulation, and due to the decrease in the bulk density of the
Australian goethite/limonite ores (Australian ores can contain packed sinter bed after charging). The beneficial effect of RF-
significant levels of goethite (Loo and Ellis, 2014)), generally MEBIOS on sinter productivity was confirmed on Number 3
divided into Marra Mamba and pisolitic ores, in the raw mix sinter plant in the NSSMC Kashima Steel Works, and it has
(Kawaguchi and Usui 2005; Kasai et al. 2005). The objective is now been installed on three commercial sintering machines
to utilize large amount of fine ores by controlling the void (Kashima, Wakayama and Kokura) belonging to Sumitomo
structure of the sinter bed structure (improving permeability Metal Industries Ltd (Lu and Ishiyama, 2015).
of sinter bed and sinter yield).
As a result of the project a new agglomeration concept was
defined, and was known as MEBIOS (Mosaic Embedding Iron 3.3. Composite Agglomeration Process (CAP)
Ore Sintering) (Hayashi et al. 2009). The MEBIOS process
organizes dense granulated pellets (ageing bed) in a conven- The exhaustion of high grade deposits has increased the
tional sinter mixture (induction bed). In this way, well-devel- utilization of domestic iron ores (low grade and small scale).
oped voids and few pores create a ventilation route These ores are typically transformed into fine grained con-
(Otomo et al., 2009; Kamijo et al., 2013) (see Figure 2). The centrates by grinding and beneficiation, and that has caused
ageing bed is based on Marra Mamba ore (consisting of fine an increase in the supply of fine grained concentrates (accom-
panied with imported fine grained concentrates increase). If
this kind of ores is used to produce pellets, pelletizing plants
are necessary to be built. However, pelletizing plants construc-
tion is restricted as a consequence of the stability of iron ore
sources, current overall arrangement and investment and the
difficulty of pelletizing plants to be able to treat all kinds of
iron raw materials (Jiang et al., 2010a). Nowadays, fine con-
centrates are used to produce sinter along with coarse grained
iron ores, and this causes a certain deterioration of the sinter
production because fine concentrates impairs sinter bed per-
meability. Sinter and pellets are used together in blast furnace
(Jiang et al., 2010a), but there are several drawbacks, mainly:
spherical shape of pellets (lower angle of repose than sinter,
and for that reason higher tendency to flow toward the center
of the furnace, causing unstable operation), and the higher
bulk density of pellets that makes them to sink into the coke
layer during burden descent (Jiang et al., 2010a). Jiang et al.,
2010a developed the Composite Agglomeration Process as a
method to overcome the problems associated with the sphe-
rical shape of pellets and the increase in the supply of fine
grained iron raw materials.
Figure 2. Illustration of the mosaic embedding iron ore sintering process The process is schematized in Figure 3. The basis of the
(MEBIOS process). process developed by Jiang et al., 2010a is:
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 219
(1) Part or all of fine grained iron raw materials suitable 4. Flame front
for balling are transformed into 8-16 mm green pel-
Flame-front speed has a large influence on sinter quality,
let; the rest of fine grained and coarse fine ores,
productivity and sintering time (Zhou et al. 2015). The
fluxes, fuels and return fines are mixed and granu-
flame-front is the region where coke particles are combust-
lated (primary mixture).
ing, having two borders, where coke begins to combust in
(2) Green pellets and primary mixture are blended
the initial one and is burned out in the opposite (Loo 2000).
(secondary mixture), and that secondary mixture is
However the temperature at which coke particle starts to
then fed onto the sintering machine.
combust depends on size, oxygen partial pressure, volatile
(3) The mixture is transformed into the composite
content and component types in the coke. The temperature-
agglomerate (composed by basic sinters and acid
time profiles are measured by means of thermocouples
pellets, where acid pellets are embedded in basic
embedded in the sintering bed. Other authors suggest that
sinter) by ignition and down draft firing.
the flame-front is the area where coke did not reach the
(4) The composite agglomerate is crushed and
combustion temperature, defining a border between com-
screened, and fraction <5 mm is considered return
busted zone and initial mix of raw materials (Yang et al.
fine and sent back to the beginning of the process.
2006). Zhao in 2012 suggested that flame front is the zone
where the coke combustion rate is greater than 1%
CAP was put into practice firstly at Baotou Iron and Steel (Zhao 2012). Raising flame front temperature increases air-
Company in 2008. CAP improved sinter bed permeability, flow resistance and leads to longer sintering times and a
decreased fuel consumption, and increased productivity of lower productivity (Nakano et al. 2010), also speeding up
sinter machine (Jiang et al., 2012). This process is similar to the flame-front is achieved by increasing the airflow rate
MEBIOS that displays its predominance on efficiently using (increasing heat transfer down to bed and oxygen level in
low-grade iron ores and limonite (with high productivity and the gas) (Zhou et al. 2015). Flame front speed from 23.9 to
reducibility, but also enhancing sinter strength) (Jiang et al., 27.7 mm/min increases productivity without affecting sinter
2015). strength, but higher flame front speeds (> 27.8 mm/min)
Zhang et al., 2011 studied the use of CAP to specularite deteriorates productivity, sinter size, and strength
ore. Jiang et al., 2015 studied the application of CAP to (Zhou et al. 2015). The ideal flame front profile in the
prepare blast furnace burden materials from titanomagnetite sintering process is shown in Figure 4. Heating time in
concentrate. the high temperature zone (above 1100°C) should be short
Iron concentrates containing fluorine is a typical inferior (1.5 min). The reason is that partial oxygen pressure in this
sintering material with very low Tumbler Index and pro- zone is low as a consequence of coke combustion and FeO
ductivity. Jiang et al., 2010b studied the effect of CAP on formation (harmful for sinter reducibility). On the contrary,
fluoric iron concentrates sintering. Jiang et al., 2010b cooling time (from maximum temperature down to 1100°C)
observed an improvement in the yield and quality of the should be long (3-5 min) with the purpose of avoiding a
sinter. strong sinter structure by the formation of a gangue matrix.
220 D. FERNÁNDEZ-GONZÁLEZ ET AL.
that contained significant levels of calcium ferrite and reox- SFCA formation increases when the Al2O3/SiO2 ratio
idized hematite and less magnetite (which is in agreement increases (Kim et al. 2002).
with Wang et al., 2016 as they observed that magnetite was An important aspect of sinter formation is the variation in
almost totally eliminated during slow cooling for sintered partial pressure conditions with temperature at different
samples with 0.5% and 5% O2) and glassy silicate. Wang stages of the sintering process. Wang et al., 2016 illustrated
et al., 2016 also observed that SFCA was produced during this aspect in the sinter process by the comparison of micro-
cooling via crystallization from a silicate melt at high tem- structures of commercial sinter to the laboratory generated
peratures, being strongly promoted the formation of SFCA sinters. Wang et al., 2016 studied the effects of sintering
when slow cooling in an oxidizing gas atmosphere (Webster temperature, CaO/SiO2 ratio, sintering gas atmosphere and
et al., 2012, observed that during cooling form 1350°C to 25° cooling procedure on the formation of mineral phase during
C, the first phase to crystallize by reaction between Fe3O4 and the sintering process, with special interest in the SFCA. Wang
melt was and Fe-rich SFCA phase with composition similar to et al., 2016 observed that SFCA content is affected by tem-
SFCA-I in synthetic iron ore sinter mixtures). Fan et al., 2011 perature increasing in the range of 1250-1300°C
observed a calcium ferrite (CF) strong ability of precipitation (further increasing in sintering temperature causes SFCA
during the sintering process (CF could crystallize rapidly at a decomposition by reduction of Fe3+ to Fe2+ in the SFCA
cooling rate of 150°C/min, and decreasing cooling rate favors crystal structure). Wang et al., 2016 also verified that slow
the development of the crystal) which is in agreement with cooling in an oxidizing gas atmosphere strongly promoted
Ding et al., 2016. The needle-like CF has good strength, SFCA formation. Wang et al., 2016 concluded that increasing
excellent reducibility, and low temperature formation (Fan CaO/SiO2 ratio and oxygen partial pressure favor SFCA for-
et al., 2011). Low sintering temperature favors the formation mation. They stated that increasing partial oxygen pressure
of acicular calcium ferrite during heating (an increase in promoted SFCA formation by stabilizing Fe2O3 relative to
heating temperature and time promotes the transformation Fe3O4. Although Wang et al. 2016 did not distinguish in
from acicular type through columnar to irregular) (Hsieh and their analysis between the two types of SFCA phases, their
Whiteman 1989b). Acicular calcium ferrite can be also formed observations on the effect of partial oxygen pressure agrees
during cooling according to Hsieh and Whiteman 1989b, with Webster et al., 2013 in higher partial pressure being
being both options necessaries in order to improve sinter preferable (if low oxygen partial pressure, SFCA-I is not
properties. Ding et al., 2016 studied the non-isothermal crys- formed). Webster et al., 2013 found that SFCA-I (the pre-
tallization kinetics of 2CaO·Fe2O3 and CaO·Fe2O3 and ferred phase) does not form at low partial oxygen pressure
observed that increasing the cooling rate promotes (at 1·10–4 atm), and at too high partial pressure the stability
CaO·Fe2O3 crystallization but inhibits 2CaO·Fe2O3 crystalliza- field of SFCA-I, the precursor phase to SFCA, is reduced.
tion. This aspect is beneficial during sintering as it was pre- Jeon et al. 2010 found the following reaction rate of iron
viously mentioned. oxide (Fe2O3) with lime for the formation of dicalcium
Higher temperatures than 1200°C, the main reaction is ferrite: FeO > Fe3O4 > Fe2O3. In this way, Fe2O3 is reduced
solid-liquid. The presence of a molten phase reinforces the to Fe3O4 and FeO before the calcination of limestones
formation of ferrites: beginning, as a function of the partial pressure of oxygen
(determined according to the CO content in the CO+CO2
CaO Fe2 O3 þ Al2 O3 þ SiO2 ! CaO SiO2 ðFe; AlÞ2 O3 reducing mixture) (Jeon et al. 2010).
Yin et al., 2013 studied the formation behavior of calcium
Scarlett et al. 2004 showed the sequence of reactions
ferrite in solid state below 1200°C when calcium hydroxide
followed to obtain SFCA by sinter mixtures. In this research,
and calcium carbonate are used as CaO sources. They
it is said that the presence of alumina increases the tem-
observed the formation of both Ca2Fe2O5 and CaFe2O4
perature at which CF and C2F initially form. Moreover, it is
when Fe2O3 and either CaCO3 or Ca(OH)2 are used as start-
mentioned that silica (quartz) reacts with neither Fe2O3 nor
ing materials, with the formation of Ca2Fe2O5 tending to be
CaO, and remains inert until SFCA and SFCA-I begin to
prior to CaFe2O4 at lower temperatures (<900°C). Yin et al.,
form at around 1050°C (Scarlett et al. 2004). Alumina addi-
2013 observed that calcium ferrite formation is related to the
tion (up to 5%) decreased the formation temperatures and
starting CaO sources, and for that reason they found that
increased the formation rates of SFCA and SFCA-I (Scarlett
formation rates of CaFe2O4 were higher when CaCO3 was
et al. 2004). Maeda et al. 2004, studied CF, CF + Al2O3 and
used as CaO source.
CF + SiO2 samples. The presence of alumina is effective to
Iron oxide can simultaneously be reduced by carbon mon-
dissolve the hematite in CF, and the addition of SiO2 is
oxide (from partial combustion of coke-coal) (Egundebi and
effective to raise the CF formation rate (Maeda et al. 2004).
Whiteman 1989; Rojas and Barraza 2008). Fe3O4 can oxidize
Kim et al. 2002, studied CF2, CF2 + Al2O3 (3-9%) and CF2 +
to Fe2O3. FeO can oxidize to Fe3O4 or Fe2O3, and can initiate
SiO2 (1-7%) samples sintered to prepare SFCA. Alumina
with outside energy (carbon or solar), low melting point slag
solubility in CF2 at 1250°C is 5-7% and silica solubility is
formation reactions (Egundebi and Whiteman 1989; Ruiz-
2-4% (Kim et al. 2002). Monoclinic structure CF2 changes to
Bustinza et al. 2013; Mochón et al. 2014b):
triclinic when it reacts with Al2O3 and SiO2 to form SFCA
(Kim et al. 2002). The addition of SiO2 at 1200°C causes
partial decomposition of CF2 into calcium silicates (Kim FeO þ SiO2 ! SiO2 FeO 1180 C
FeO þ CaO þ SiO2 ! CaO SiO2 FeO1223 C
et al. 2002). Moreover, hematite formation decreases and
224 D. FERNÁNDEZ-GONZÁLEZ ET AL.
Silica from the iron can react with molten ferrite to form down to form SFCA and hematite at temperatures higher
calcium silicates and precipitate hematite or magnetite, than 1220-1240°C.
depending on the oxygen partial pressure in the reaction As it was mentioned, sintering process converts fine iron
system, together with the silicate formed (Matsuno 1979; ores into suitable lumpy agglomerates. Sinter is composed by
Matsuno and Harada 1981): three phases: iron oxides, calcium ferrites (silicon ferrite of
calcium and aluminum, SFCA) and silicates. SFCA is a desir-
CaO Fe2 O3 þ SiO2 ! CaO SiO2 þ Fe2 O3
able bonding phase that plays an important role in strength
Blended particulate bed on the sinter strand is partially and reducibility. Sinter mixture includes several types of ores,
melted in the flame front to give a multiphase system com- fluxes, fuels and return sinter fines, and as a consequence of
posed by solid, melt and gas. The mix coalesces, changes its the large variation of particle size (which is detrimental to the
shape and aggregates to form dense clusters in presence of bed permeability) the mixture should be granulated to have a
melt. After the flame front, a solidified bed of dense clusters, quasi-particle before charging onto the sinter strand
which is crushed at the end of the strand with the purpose of (Fernández-González et al., 2017). Jeon et al., 2015 studied
achieving the granulometry mentioned previously, is the utilization of magnetite concentrate as an additive in
obtained. The coalescing behavior of the molten mix formed adhering fines of quasi-particle and the effect of magnetite
in the flame front is responsible of the size, density, and addition on assimilation behavior. Jeon et al., 2015 observed
strength of the sinter as Liu and Loo 2016 said. In Figure 5 that a small addition of magnetite significantly affected the
it is possible to see the development of the sinter structure. physicochemical properties of melt and final sinter micro-
Coalescence strongly depends on the volume of melt in the structure (more SFCA was formed with fixed CaO because
mix that also depends on the properties of iron ore in the mix Fe2+ (of the magnetite) directly replaced Ca2+ in the substitu-
(Liu and Loo 2016). In this context, unless a certain level of tion mechanism of SFCA). Jeon et al., 2015 also concluded
coalescence is reached, the sinter product will not have suffi- that the assimilation behavior was improved with the proper
cient size to be fed into the blast furnace, but also will not addition of magnetite in adhering fines of quasi-particle. Jeon
have enough strength (Liu and Loo 2016). Liu and Loo 2016 et al., 2014, studied the utilization of high Al2O3 pisolitic ore
studied the melt properties on coalescence. They observed in sintering process. They designed a quasi-particle where the
that iron ore size and its initial densities govern the densifica- pisolitic ore is used as nuclei and ultrafine hematite and
tion process in solid state. Liu and Loo 2016 observed that the magnetite ores are used as adhering fines. Jeon et al., 2014
ore type has influence on liquid phase sintering (porous ore is observed that the quasi-particle comprising high Al2O3 piso-
the most effective, as it is more readily to form a more litic ore and ultrafine magnetite ore had competitive sinter
deformable system). Higher levels of porous ore and return quality (similar to the quasi-particle sample consisting nuclei
fines in sinter mix facilitates coalescence in flame front of dense hematite and adhering fines of ultrafine hematite).
according to Liu and Loo 2016. The increase of iron ore consumption has forced the use of
Yoshimura et al. 2009, studied the effects of adding 3-5% low quality iron ores (some low grade and high SiO2 iron
SiO2 and 3-5% Al2O3 on the penetration characteristics of ores). The high iron ores SiO2 content leads to an increase in
calcium ferrite (CF) melts into hematite sinter, varying the this compound in the sinter mixture and then of the slag
percentage of porosity (5-15%). Yoshimura et al. 2009 content of the sinter. For that reason the consumption of
observed that the penetration of CF liquid into 5% porosity serpentine containing SiO2 and MgO has to be decreased
hematite is reduced by the addition of SiO2 and Al2O3 (being and substituted by dolomite containing CaO and MgO or
the SiO2 addition more effective than the Al2O3 addition). other MgO-bearing materials with low SiO2. Zhang et al.
The penetration of CF into 15% porosity hematite was 10 2013 studied the optimal usage of dolomite in the sintering
times deeper than in the case of 5% porosity hematite process, by mixing dolomite with magnetite concentrate
(Yoshimura et al. 2009), and is accelerated by the addition before granulation (improving contact condition of MgO
of SiO2, as it reduces the melting point in the calcium ferrite and FeOX could increase the solid solubility of MgO in the
system. Yoshimura et al. 2009 checked that the ratio between magnetite, thus decreases the MgO content in calcium ferrite,
surface tension and viscosity of melts dominated the penetra- and for that reason increases the fluidity of the bonding phase
tion depth of CF-based melts. and sinter strength) and by using dolomite with mean size of
Patrick and Pownceby 2002, researched the SFCA sta- 1 mm (could decrease the dispersity of MgO in the sinter
bility between 1240 and 1390°C in air. Specimens of SFCA mixture, decreasing the negative influence of MgO on the
where prepared from mixtures of four ores in the Fe 2O3- fluidity and bonding capacity of the bonding phase).
CaO-Al2O3-SiO2 system (Patrick and Pownceby 2002).
The lower temperature limit of 1240°C was selected on
7. Conclusions
the basis that is the lowest anticipated SFCA melting
temperature (Patrick and Pownceby 2002), and it is esti- A review of the history of the sintering machines has been
mated that SFCA solid solution will completely decompose done. Nowadays, Dwight-Lloyd is typically used in the main
at around 1480°C (Patrick and Pownceby 2002). Webster sinter plants.
et al., 2013 observed that the temperature stability of Sintering is performed after the granulation process, and
SFCA in air range from 1173°C to 1321°C, while similarly allows obtaining a product > 20 mm to be used in the blast
SFCA-I in air range from 1143°C to 1321°C. Scarlett et al., furnace as burden material. New alternative processes to sin-
2004 observed in vacuum experiments that SFCA-I breaks tering and pelletizing have being studied in this paper: HPS
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 225
(Hybrid Pelletized Sinter, to produce sinter from pellets); and and Materials Society), San Diego, CA, February 27-March 3, 2011,
MEBIOS (Mosaic Embedding Iron Ore Sintering, to improv- pp. 389–396.
Fan, X., Ji, Z., Gan, M., Chen, X., Yin, L., and Jiang, T., 2014, “Preparation
ing sintering when Australian goethite/limonite ores are technologies of straw char and its effect on pollutants emission reduc-
employed); CAP (Composite Agglomeration Process, combi- tion in iron ore sintering.” ISIJ International, pp. 2697–2703.
nation of the sintering and pelletizing processes to solve the Fan, X., Ji, Z., Gan, M., Chen, X., Yin, L., and Jiang, T., 2015,
problem of spheroidal shape of pellets and the increase of fine “Characteristics of prepared coke-biochar composite and its influence
grained iron ore concentrates in the market). on reduction of NOX emission in iron ore sintering.” ISIJ
International, 55, pp. 521–527.
Flame front defines the sintering process and has large Fernández-González, D., Martín-Duarte, R., Ruiz-Bustinza, I., Mochón,
influence on sinter bed structure, being the SFCA J., González-Gasca, C., and Verdeja, L. F., 2016, “Optimization of
(Silicoferrites of Calcium and Aluminum) component the sinter plant operating conditions using advanced multivariate statis-
one that gives the best characteristics of reducibility, Shatter tics: Intelligent data processing.” JOM, 68, pp. 2089–2095.
index and Tumbler index. Reactions that take place during the Fernández-González, D., R., Ruiz-Bustinza, I., Mochón, J., González-Gasca,
C., and Verdeja, L. F., 2017, “Iron ore sintering: Raw materials and
sintering process and how they influence in sinter quality have
granulation.” Mineral Processing and Extractive Metallurgy Review 38,
been also reviewed. pp. 36–46.
Ferreira, S., Cores, A., Robla, J. I., Verdeja, L. F., Ruiz-Bustinza, I.,
García-Carcedo, F., and Mochón, J., 2014, “The influence of gangue
Acknowledgments and additives on the divalent iron content of magnetite pellets.” Steel
Research International, 85, pp. 261–272.
This research was supported by the Spanish Ministry of Education, Formoso, A., Moro, A., Fernández-Pello, G., Menéndez, J. L., Muñiz, M.,
Culture and Sports via an FPU (Formación del Profesorado and Cores, A., 2003, “Influence of nature and particle size distribution
Universitario) grant to Daniel Fernández González (FPU014/02436). on granulation of iron ore mixtures used in a sínter strand.”
The authors wish to thank the CENIM-CSIC for their cooperation in Ironmaking and Steelmaking, 30, pp. 447–460.
conducting the investigation. Fujino, K., Murakami, T., and Kasai, E., 2013, “Effect of utilization of
metallic Fe particles as an agglomeration agent on the permeability of
sintering bed.” ISIJ International, 53, pp.1617–1624.
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