Influence of magnesia on sintering

characteristics of iron ore

U. S. Yadav, B. D. Pandey, B. K. Das, and D. N. Jena

The MgO in blast furnace slag provides an optimum

condition in terms of both good flowability and
desulphurisation. The mode of its addition to the
blast furnace changed from, initially, as raw flux
in the form of dolomite, to via sinter, with the
argument that raw flux demands energy for its
decomposition inside the blast furnace. Thus, the
decomposition reaction was diverted from the blast
furnace to the sintering bed, and the energy source
for decomposition was changed from costly blast
furnace coke to a relatively cheap coke breeze. Now
olivine/dunite/serpentine is being used as a source
of MgO, where energy for decomposition is not
required; this also provides a source of SiO2 , which
eliminates need for the addition of quartzite. The 1 Influence of MgO on productivity
effect of MgO on blast furnace slag is fairly well
established, but its effect on sintering and sinter
quality is unclear. Operating results of the sinter energy for decomposition is not required; this also provides
plants show that, with an increase of MgO, the a source of SiO 2 , which eliminates need for the addition of
sintering rate, the fuel rate, and sinter strength and quartzite. The eVect of MgO on blast furnace slag is fairly
reducibility deteriorate; however, high temperature well established, but its eVect on sintering and sinter quality
properties such as the reduction degradation index is unclear. Numerous exhaustive laboratory studies1 –1 9 have
and the softening–melting characteristics of the been compiled to investigate the subject, but views remain
sinter improve. The present work attempts to divided. The present work attempts to establish the in uence
establish this influence on the sintermaking process of MgO on the sintermaking process and product quality
and sinter quality with the help of operating plant with the help of operating plant data from sinter plant 2
data. I&S/1595 (SP2) at Tata Steel. Some basic information on the design
and capability of SP2 is given in Table 1.
Dr Yadav is in the Ironmaking Technology Group, Mr Pandey is
in the Research and Development Department, and Mr Das and
Mr Jena are at sinter plants BB and SP2, Tata Steel, Jamshedpur,
RESULTS AND DISCUSSION
India. Manuscript received 25 January 2001; accepted 27 June Influence on sintering rate
2001.
Analysis of the monthly average plant data between April
© 2002 IoM Communications Ltd. 1994 and March 2001, shown in Fig. 1, indicates that with
an increase of MgO the plant productivity decreases.
Magnesium minerals are known to be diYcult materials
for assimilation;8 in the highly  uxed composition MgO
INTRODUCTION acts as a refractory phase1 3 and the magnesium remains
Sinter, being the preferred blast furnace burden, has attracted either in relicts or in reaction zones. The MgO can form a
the attention of both producer and customer alike, along melt with SiO2 at temperatures >1350°C and with Fe2 O 3
with scientists and researchers in the Ž eld. Requirements at >1600°C, i.e. the addition of MgO increases the liquidus
to produce a higher tonnage with consistent and superior
quality, at a lower cost, have brought all aspects of the pro- Table 1 Salient features and specifications of sinter
duction process under critical reexamination.The chemistry plant 2
is the parameter that is easiest to check, and studies have
focused on the control of this by various means. The pros Plant capacity (rated) 1·37 Mt/annum
and cons of the in uence of each constituent have been Present production 2·33 Mt/annum
Sintering area 192 m2
repeatedly investigated. Depth of sinter bed 600 mm
Ever since it has been known that MgO provides an Pallet width 3m
optimum blast furnace slag condition in terms of both good Strand length 64 m
 owability and desulphurisation, it has been a desirable Mixing drum size 3·8 m dia. Ö 15 m length
Mixing drum capacity 450 t h – 1
constituent of blast furnace  ux. The mode of addition Cooler type Circular; dip rail
changed from, initially, as raw  ux in the form of dolomite, Cooling area 140 m2
to sinter  ux, with the argument that raw  ux demands Cooler capacity 335 t h – 1
energy for its decomposition inside the blast furnace. Thus, Waste gas fan (max. pressure) 148 mbar
Cooler fansÖ 2 (max. pressure) 25 mbar
the decomposition reaction was diverted from the blast Combustion fansÖ 2 (max. pressure) 70 mbar
furnace to the sintering bed, and the energy source for Waste gas volume 929 000 m3 h – 1
decomposition was changed from costly blast furnace coke Outlet gas dust loading 100 mg (Nm) – 3
to a relatively cheap coke breeze. Later, olivine/dunite/ Suction at grate bar 1450 mm Hg
Air for ignition From cooler
serpentine was found to be a better source of MgO, where
DOI 10.1179/030192302225002018 Ironmaking and Steelmaking 2002 Vol. 29 No. 2 91
92 Yadav et al. Influence of MgO on sintering of iron ore

(a )

2 Influence of MgO on coke breeze rate

temperature of the melt, resulting in a decrease of the

sintering rate.9 ,1 2 ,1 4 ,1 8 Also, the comparatively poor sintering
behaviour of MgO and poor bond strength among the
sintered particles result in increased return Ž nes, decreasing
the productivity.

Influence on fuel rate (b )

An increase in MgO content in the sinter increases the
coke breeze rate, as shown in Fig. 2. This increase in coke
breeze rate may be attributed to the refractoriness1 3 of the
MgO phase and its poor assimilation behaviour,8 which
demand a higher heat input to obtain the desired melt a +6·3 mm; b ­ 0·5 mm
level. Studies4 conŽ rm that an increase of sinter MgO/CaO 3 Influence of MgO on tumbler index (TI) for given
ratio results in less melt formation and contributes to an fractions
increase in the liquidus temperature. The CaO and Fe2 O 3
form a melt (calcium ferrite, monocalcium ferrite, or dicalcium
ferrite) at ~1150°C, and in the presence of impurities at
the major mineral constituent of the sinter structure, which
even lower temperatures. As well as increasing the liquidus
binds the melting and unmelting parts (relict hematite, etc.),
temperature of the melt phase, the higher MgO also results
and imparts strength to the sintered mass. Owing to the
in increased melt viscosity. A higher viscosity melt would
thermal expansion – contraction between the glass phase
have a limited  owability1 6 into spaces between particles,
and the crystalline phase it encloses, the vitreous glass
and limited binding therein. This suggests that, for normal
exhibits a high degree of stress. The MgO addition suppresses
liquid formation with lower viscosity necessary for the
the formation of calcium ferrite and increases formation of
required bonding, the process demands a higher heat input.
the vitreous glass matrix and dicalcium silicate in certain
As sintermakers maintain proper bonding in the product
slag pools. These structures are harmful for sinter strength,
sinter by adjusting the coke breeze rate, this explains the
and therefore result in a remarkable drop in sinter tumbler
results illustrated in Fig. 2. Conceptually, the addition of
index. At 697°C, the dicalcium silicate undergoes an allotropic
MgO, by raising the basicity ((CaO +MgO)/SiO 2 ), should
transformation from b-2CaO.SiO 2 to c-2CaO.SiO 2 ; this is
lower the sintering temperature, but the results of actual
accompanied by a volume change and stress development,
experiments7 ,1 0 have shown a 30–60 K higher sintering tem-
making the resulting sinter brittle and liable to dusting
perature for specimens containing 3·33–5·86% MgO than
under load. With an increase of the MgO/CaO ratio, the
for similar specimens but without MgO. The higher coke
amount of ferrite and hematite decreases with a concomitant
breeze rate is the very obvious requirement of a higher
increase in magnetite content. Magnetic susceptibility or
sintering temperature.
magnetic index is proportional to the magnetite content
of the sinter, which is related to the sinter strength.2 The
Influence on strength in uence of MgO on the tumbler strength of sinter under
The tumbler index (TI ), which represents the room temper- actual operating conditions is shown in Fig. 3. Surprisingly,
ature strength of the sinter and gives an indication of its in contrast with theoretical explanations, with increasing
disintegration behaviour during handling, has been found MgO the tumbler index improves. This unexpected behaviour
to be in uenced by MgO. of the plant sinter under consideration is because the drive
In acidic sinters with up to 4% MgO addition the tumbler to make stronger sinter necessitates extra coke addition.
strength increases. This has been attributed3 to the high Figure 4 shows the eVect of sinter MgO on the cumulative
degree of recrystallisation in the glass phase with precipitation +10 mm and ­ 5 mm fractions and the mean size of the
of pyroxene and olivine. Further MgO addition results in product sinter. It can be seen that, with an increase of
a drop in strength value, mainly on account of (a) a vitreous MgO, the cumulative +10 mm fraction and the mean size
glass matrix, which is believed to exhibit a high stress of the sinter increase, but its in uence on the ­ 5 mm
concentration, and (b) low melt formation during sintering fraction is unclear. Theoretically, these illustrations should
as indicated by the high porosity of such sinters. show a reverse trend, owing to the poor sinterability and
In self- uxing and super uxed sinters, the tumbler index limited melt formation characteristics of MgO translating
decreases with the addition of MgO.2 , 3 , 7 , 9 , 1 1 , 1 2 , 1 4 The sinter to poor bonding and cold strength arising from the decreased
matrix is deŽ ned as the sum of the glass, silicates, olivine, proportion of slag binder in the mineralogical composition
and calcium ferrite in terms of volume. Calcium ferrite is of the sinter. The diVerent behaviour of the plant sinter
Ironmaking and Steelmaking 2002 Vol. 29 No. 2
 Yadav et al. Influence of MgO on sintering of iron ore 93

(a )

5 Influence of MgO on reduction degradation index (RDI)

monthly plant data provides a similar observation, as shown

in Fig. 5, although this is the net result of several factors
including MgO and the requirement for a low RDI sinter
for the blast furnaces. In fact, a low RDI sinter is being
(b )
produced by changing operating practices at the expense
of a high coke rate.

Influence on reducibility
The in uence of MgO on reducibility characteristics is
shown in Fig. 6. It can be seen that the reducibility of the
sinter increases with a decrease of sinter MgO. The negative
in uence of MgO addition on the reducibility of iron ore
sinter3 ,7 , 9 ,1 0 ,1 3 is believed to be a result of the decrease in
hematite and calcium ferrite phases and increase in magnetite
phase having lower reducibility. During sintering, MgO
accelerates the thermal decomposition of Fe2 O 3 and favours
the formation of a spinel structured Fe3 O 4 (FeO.Fe2 O 3 )
phase. This is gradually replaced by a spinel type solid
(c ) solution of magnesioferrite, (Fe,Mg)O.Fe2 O 3 , by substituting
FeO and MgO between magnetite grains. The addition of
MgO causes the disappearance of the calcium ferrite and
brings about an increase in the content of MgO bearing
olivine (more forsteritic member of the isomorphous mixture
a cumulative +10 mm; b ­ 5 mm; c mean size forsterite–fayalite) and the appearance of almost irreducible
4 Influence of MgO on given fractions and mean size of pyroxene and ferromonticellite.1 0
product sinter As mentioned above, an increase of MgO/CaO ratio
decreases the amount of ferrite and hematite with a
concomitant increase in the magnetite content. Since the
magnetic susceptibility, or magnetic index, of the sinter
from that expected from theory may be explained by the is proportional to its magnetite content, as the magnetic
result of use of extra coke breeze, which overrides the index increases there is a drop in the reducibility. Hence,
adverse eVect of MgO variation.

Influence on reduction degradation index

The MgO content of the sinter in uences its reduction
degradation index (RDI). It has been argued that, at low
basicity, the addition of MgO decreases the hematite content3
and increases the formation of magnetite and magnesia
spinel (MgO.Fe2 O 3 ) (Ref. 9) from magnesia and hematite
in the resultant sinter, at the expense of hematite,1 resulting
in an improvement in RDI. Higher magnetite and magnesia
spinel or lower hematite contents are known to be respon-
sible for lower degradation. However, at higher basicity,
even without MgO, in spite of higher hematite, the sinter
RDI is low. This is a result of the sinter structure at higher
basicity, which is distinguished by a continuous ferrite frame
capable of arresting the propagation of cracks initiated at
the hematite crystals. Also, the substitution of CaO by
MgO results in a higher sinter FeO, thus having an eVect
equivalent to that of the coke addition. The analysis of 6 Influence of MgO on reduction index (RI)

Ironmaking and Steelmaking 2002 Vol. 29 No. 2

94 Yadav et al. Influence of MgO on sintering of iron ore

with the addition of MgO, the less reducible magnetite in favour of olivine and pyroxene at MgO/CaO å 0·6. At
phase appears in increased amounts at the expense of basicities å 1·3, increased MgO addition favours the formation
highly reducible hematite and ferrite phases. This explains of glass. Most of the CaO taking part in the formation of
the increase in RDI value as well.2 calcium ferrite is released as MgO replaces CaO. The
At a constant coke rate, with an increase of MgO/CaO released CaO takes part in the formation of slag along
ratio, owing to less melt formation, the porosity increases. with the other slag forming constituents.
This should increase the reducibility and the RDI value
sharply.4 This is supported by Moukassi et al.,5 who doped
Influence on porosity
wustite with magnesium and reported an accelerated rate
of reduction. However, plant data (Fig. 6) do not support An increase in MgO content of the sinter increases the
this aspect, perhaps because of diVerences between experi- total porosity, which can be explained by the properties
mental conditions4 , 5 and the present analysis (plant data). and amount of the melt during sintering.1 6 It can be argued
that, with an increase of MgO, the amount of melt formation
decreases and the viscocity of the melt formed increases.
Influence on softening–melting characteristics Under interfacial forces, the lower amount of  uid with a
Experiments carried out with pot grate sinter made at higher viscosity will have a limited  owability into the spaces
Tata Steel’s R&D laboratory as well as with Tata Steel between particles. Thus, there will be a limited capability
plant sinter have established the in uence of MgO on its to draw the particles together, resulting in minimal shrink-
softening–melting behaviour. It has been reported that, age. It is therefore expected that sinters with high MgO
with an increase of MgO, the softening–melting character- contents will have higher porosity.
istics of sinter improve.6 ,7 ,1 7 ,1 9 Experimentation at BSC
Laboratories, UK, carried out on laboratory sinter made Influence on abrasion resistance
at Tata, established1 9 that by changing the sinter MgO The literature reveals that an increase in MgO content of
from 2·3 to 3·2% the softening start and melting start tem- the sinter decreases the abrasion resistance. This has been
peratures change from 1305 to 1391°C and from 1467 to attributed to the increased viscosity of the melt owing to the
1525°C, respectively. The softening–melting range decreases presence of MgO and the increased amount of magnetite,
from 177 to 166 K, the residuals decrease from 8·8 to 1·7% , both known to contribute to poor abrasion resistance of
and the maximum pressure drop across the softening–melting the sinter.1 1 An increase of the MgO/CaO ratio lowers the
bed decreases from 15·2 to 5·3 kPa. Studies6 ,7 of phases abrasion resistance because of its inverse relationship with
associated with sinter (in relation to CaO–SiO 2 –MgO– porosity.4
Al2 O 3 and CaO–Fe2 O 3 –MgO systems) indicate that, with
an increase of MgO content, the liquidus temperature of
dicalcium silicate increases and the calcium ferrite phase CONCLUSIONS
changes to calcium–magnesioferrite, thus improving the 1. Magnesium minerals are known to be diYcult materials
softening–melting behaviour of the sinter. for assimilation, and MgO acts as a refractory phase during
sintering. It increases the liquidus temperature of the melt,
resulting in higher heat demand and decreased sintering
Influence on mineralogical modifications rate.
The addition of MgO reduces the dispersion of CaO 2. The addition of MgO suppresses the formation of
in sinter. Microprobe analysis conŽ rms that, when MgO calcium ferrite and increases that of dicalcium silicate and
is added to the sinter mix, most of the Mg2 + enters the the vitreous glass matrix, which exhibits a high degree of
magnetite lattice to form magnesiospinels of the type stress. These structures are harmful for sinter strength, and
(Fe,Mg)O.Fe2 O 3 by displacing Fe2 + ions from the magnetite therefore result in a remarkable drop in its tumbler index.
lattice,2 , 3 ,1 5 and a small amount is partitioned to glass and The negative in uence of MgO on strength and granulometry
SFCA.8 Without MgO the magnetite (FeO.Fe2 O 3 ), which can be corrected by extra coke addition.
has a spinel structure, exists in pure form, but is replaced 3. The addition of MgO accelerates the thermal decom-
by a mixed spinel of type (Fe(1 – x ) Mgx )O.Fe2 O 3 (x ­ 1) position of Fe2 O 3 and favours formation of the less reducible
with MgO addition, conforming to the system MgO.Fe2 O 3 . Fe3 O 4 (FeO.Fe2 O 3 ) phase. Also, MgO addition restricts
The ionic radii of Mg2 + and Fe2 + are similar (ionic radius melt formation, leading to increased porosity of the sinter.
of Mg2 + is 0·066 nm and of Fe2 + is 0.074 nm). As soon as Increased porosity provides more surface area exposed to
the sinter bed temperature reaches ~1000°C, by solid state the reducing gases, resulting in higher reducibility and
diVusion, the Mg2 + replaces some of the Fe2 + from the mag- reduction degradation index.
netite lattice, thus forming the mixed spinels or magnesio- 4. The addition of MgO improves the softening–melting
spinels. Like magnetite (Fe3 + (Fe2 + Fe3 + )O 4 ), magnesioferrite characteristics of the sinter. The softening and melting start
(Fe3 + (Mg2 + Fe3 + )O 4 ) has an inverse structure and exhibits temperatures increase, and the softening–melting range, the
magnetic properties,and they are optically indistinguishable residuals, and the pressure drop across the softening and
from each other. Because of the abundance of the iron melting bed decrease owing to the formation of mineralogical
oxides and the similarity of the ionic radii of Fe2 + and constituents having a higher liquidus temperature.
Mg2 + , the diVusion of Mg2 + into the lattice of these oxides,
in particular FeO.Fe2 O 3 and FeO, is much greater than
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