ISIJ International. 35 (1995), No.

Vol, 2. pp.
138-1 47

Slag Formation in the Adhering Layer of Granules and Its Reaction

with Nuclei in lron Ore Sintering

E. DACOSTA.J. P. B. VANDERHEYDEN1)
COHEUR. and R. MUNNIX1)
Facult6 des Sciences Appliqu6es, Universit6 de Li~ge, Rue ArmandSt6vart, 2.
B4000 Li~ge I Belgium.
1) Centre de Recherches M6tallurgiques.
.

1
Rue Ernest Solvay, 1, B 4000 Li~ge 1. Belgium.
(Received on MaylO. l994; accepted in final form on October 21. 1994)

This work aims at optimising the mineral phase composition of iron ore sinter to improve its properties.
At first, the conditions that favour the slag formation in iron ore sintering were studied by measuring the
conventional melting temperature. The ease of liquid phase formation was estimated in relation with the
nature of the ores and with the amountof additions.
In a second step, the reactions between slag and the iron
ore nuclei in the mix granules were studied.
For this purpose, a laboratory furnace reproducing approximately the atmosphereand thermal profile observed
in the industrial conditions was conceived. These experiments enabled to relate sinter mineral phase
composition to the process conditions and to the type of iron ore.
At last, the results obtained in the laboratory experiments were confirmed by pilot plant trials. The relations
between sinter properties and mineral phase composition were then established.
KEYWORDS:
iron ore; iron ore sinter;
adhering layer, iron ore nuclei; slag formation; conventional melting
temperature; sinter porosity; mineral phase composition: sinter properties; sinter mix design.

tions and type of reactants present in the adhering layer.

1. Introduction
Accordingly, the first step of this work presents the
The impact of sinter phase composition on sinter relationships observed betweenmelting temperature and:
properties is well known. Oneinstance is the sintering
- CaOcontent mixes of rich iron ores and limestone;
in
of binary iron ore mixes, where highly basic and acid
granules are produced separately before being mixed.1)
- CaO and Si02 contents in mixes of rich iron ores,
limestone and sand;
This technique enhancesthe sinter quality, as it has more
- CaOcontent in mixes of poorer iron ores and lime-
calcium ferrites and less vitreous phases than the normal stone.
one, for the samechemical composition. Different seg- In the second step, Iaboratory experiments were carried
regation techniques of the sinter mix taking advantage out to investigate the reactions between slag and nuclei
of the reaction CaO=Fe203 have been experimented in the mix granules allowing to associate the formation
industrially.2~6). They aim at lowering the content of of the mineral phases with the sintering conditions and
secondary hematite and vitreous phases in the product. with the type of iron ore. The parameters considered in
Consequently, a lower specific fuel consumption, a higher this work
were the mineralogy of the iron ore nuclei and
sintering yield and a better sinter reducibility have been the thermal profile of the sintering process.
observed.
To achieve these improvements, it is necessary to
understand the formation of mineral phases during the
sintering of iron ores. It consists of a very complexprocess
that, in a simplified manner, can be divided into liquid
phase (slag) formation in the adhering layer of the
granules, shownat Fig. l, reactions between the slag and
the nuclei and solidification of the products of these
reactions. Thepurpose of this work it to obtain the same
good results, based on the CaOcontent of the adhering
layer and on the mineralogy of the iron ore nuclei in
the sinter mix granules, but without using binary mixes.
The determination of the melting temperature of the
adhering layer is required for knowing the sintering
mechanisms. This temperature depends on the propor- Fig. 1. Iron ore sinter mix granule.

C 1995 ISIJ 138

 ISIJ International, Vol. 35 (1995), No. 2
In the final step, sinter pot trials confirmed the Basedon the phasediagram of the CaO-Fe203 1o) system,
laboratory results and permitted a link to be established the two following linear regressions were adjusted to
between mineral phase composition and sinter quality. determine the conventional melting temperature (CT):

2. Determination of the Melting Temperature

between 10 and 20 olo CaO:

2. 1. Experimental Method
CT= 19.57(oloCaO)+ 1625.7(r= -0.90, n=9)
-
...(1)

The technique adopted in this study to ascertain the between 20 and 40 olo CaO:
melting temperature was developed by Poot and CT=12.89(o/oCaO)+924.7(r=0.99, n= 12) ...........
(2)
Danloy.7) The equipment is similar to the
one currently An estimationof the eutectic was obtained at the
used to measure ash fusibility according to the ISO intersection of the straight lines corresponding to Eqs.
Standard 540-1974. All the experiments were carried out
with the fraction below 0.5 of the materials under a 1
(1) and (2): 21.60/0 CaOand 203'C. Such values
are
normal atmosphere. The temperature corresponding to
mm very close to those existing in the diagram CaO-Fe203.
No difference was observed between the conventional
a 2/3 reduction of the initial height of the sample is melting temperatures of the three tested iron ores. These
defined as the conventional melting temperature.
results are very similar to those found in the liter-
2.2. Mixtures of Richer lron Ores and Limestone ature. 11' 12)
The importance of the system CaO-Fe203for the iron 2.3. Mixtures of Richer lron Ores, Limestone and Sand
ore sintering process is well known. Kasai et al.8,9) Considering the very similar results obtained with the
suggested that the lowest iron ore sintering temperatures
three iron ores tested in the previous part, the following
are located between the solidus and liquidus lines of this experiments were limited to the ore B. Limestone and
system. In our experiments, the fractions below 0.5
mm sand (chemical compositions given in Table 1) were added
from three very rich iron ores, A, Band (less than olo C I to the iron ore to obtain mixes with basicity ratios
silica and alumina)
were used. Their chemical composi- CaO/Si02of 1.2, 1.6, 2.0 and 2.4 and CaO/Fe203ratios
tions are give in Table 1. Calcium oxide
was introduced of 0.12, 0.18, 0.25, 0.35 and 0.41. The CaOcontents
by mean~of limestone addition (fraction below 0.5 mm),
of which the composition is also presented in Table 9
varied between and 25 o/o and those of Si02, between
I .
4 and 190/0. The domain of investigation is shown at
In the experiments the CaOcontent was varied between Fig. 3. The obtained multiple regression equation for the
lO and 40 o/o CaO. The results are presented in Fig. 2.
1500
Tabte 1. Chemical composition of the reactants (traction
betow o.5 mm).
o
\ J,~
e
I'//'1711 /
1400
Fet
o/o
Fe2+ si02 Al203
o/o olo o/o
CaO MgO
Ol
IO
o/o
P
olo
L.0.1.
olo
'
o
:'
//
//
Il
o EquatiOn 2
Ore A 72.0 21,l 0.67 0.24 0,02
0,17 O.OIO (2.8) CL Eqvation I
Ore B 68.3 0.9 0.71 0.64 0.02 0.05 o.022 1 .O ~i300 .,,
~
,~, ll

Ore C 67.9 0.2 o54

.
0.94 0.0 1
0,05 0,049 1.7
o,
= I
ll
Ore D 68.7 0.3 l .98 o.82 0.06 0.03 0.030 l .4 ~5

Ore E
~
65.5 0.6 4.26 0.71 O.O1 0,07 0.03 l 2.0 1200
Ore F 61.2 0.2 6.73 3,03 0.05 O. 14 0,070 2.7
Ore G 60 . 8 0.5 3.66 3.95 0.06 O, Il 0,024 4.0
Ore H 56.2 0.3 6.43 3,05 0.40 0.23 0.033 10.2 5 1o 15 20 25 30 35 40 45
Cao ('/.)
Limestone o.2 O,
l 0,34 O.
14 54.63 .22 l 0,020 41,8
Fig. 2. Results of the experiments with richer iron ores and
Sand 0.7 NA 95.01 2.80 0.21 o.22 0.004 1.1
limestone (dashed lines correspond to the phase dia-
gram of the CaO-Fe203 Io) system).

\oo~c' ~30
HEMATITE
~\ / oo
\\
\ \\\\\\\~~
~t

O.41
1.2 20 1456\V).b~/b
\\ \\\ ~~1~~0,35 MAGNETITE
+~~
\ \\ 1.6-_ L~. \+~ 0.25
\ \ .1 +~. O:l

' \
2.0 + 1
+ lh \h+
\ +~ 0.18
~l\ 2.4__ ~~~L-++~-iF- +\
'l\b~C50/
/ - ~~+ \ ~ ~'+\++0.12 4500
'
10
~OO +\=-~-1\~~_~~'_
\
~ ~1~~
~~~._~-•_ ~
~(5
~;O~\ ~
~cV~ - ~~~~

Fig. 3.

o Investigation domainin the system CaO-Fe203-Si02

o o
/60
caQ ('/')
/ 70 80 90
Fe203
1OO
(o/•)
'

1-'-
139 C 1995 ISIJ
 ISIJ International, Vol. 35 (1995), No. 2
1500 1600
! Equation 1

U 1400
~~ .
Equation 3
SiO
21 150/.
O 500
1
o
Equation
Equation
Equation
Equation
2
3
4
5
el
,
Si02 1O o/.
~ 'a!II I
SI02 = 5 '/o (1)

1400 ;1~ •'

~F ~ g)dll
e,~
Equation
/1 D
~ l /la
JLo;/ J:A
E1 ~
300 e, '
al /1/
JL
~ A c
i 300 ~L'AIA
o) ~;
E oE~.;1'i'
I
Si02 between 2 5 and
AD D ~
'l)
:~
1200 7.
4 •/-

1200 ~\see~t\+
D Si02 between 75 and 12,4 "/- =
o
A Si02 between 12 5 and 19 O'/- (J

11oo
11oo 11OO 1200 1300 1400 1500 1600
5 1o 15('/.) 20 25
cao Measuredmelting temperature f'C)
Fig. 4. Results of the experiments with richer ores, Iimestone Fig. 6. Measured and calculated conventional melting tem-
and sand. perature.

1600 level in the adhering layer must be kept.

2.4. Mixtures of Poorer lron Ores and Limestone
O 1500 e This series of experiments was carried out with 21
\e, Equation 2 mixes, using 3poorer iron ores F,
o
\\ ~I"~~' and (silica contents G H
=
(1'
dl between 3.8 and 7o/o, and alumina contents between 3.l
Equation4
o
a 1400 h'
e
I "' and 4. I olo). The chemical compositions of these ores are
E
o
Itl

1lb
given in Table 1. The results obtained are given in Fig.
~
Q, ~Ib::.~\I~
///// l
= ee
IblL\I~LI:~'
.
..'
5and the corresponding multiple regressions are:
~5 Equation I /
'

~ 1300
'IP" Equation 5
~
!~ .lI between 10 and 25o/o CaO:
CT= 15.88(o/oCaO)+ 1627.8(r= -0.97,
- n= 12) .(4)

1200 .
,1
1
d

between 25 and 40 olo CaO:

5 10 15 20 25 30 35 40 45
CaO
Fig.
I'/•)
CT=14.16(o/oC.aO) + 852.3 (r=0.99, n =9) .............(5)
5. Results of the experiments with poorer ores and
limestone. The straight lines corresponding to these two equations
are shown at Fig. 5, comparedto the results obtained
conventional melting temperature is: with the richer ores. In this case, the two regression lines
have their intersection at 213'C and 25.5 o/o CaO. The 1
CT=- 22.26 (oloCaO) + 0,38 (oloCaO oloSi02) •
mixes of richer ores without Si02 addition showa lower
+ 1659(r=0.98, n=20) ............................(3) CaO content at the minimum melting temperature
(21 .6 olo). Theresults also showthat these mixes of richer
The lines corresponding to this equation for 5, 10 and
15 o/o Si02 and also to Eq. (1) are presented at Fig. 4. In ores, with CaOcontents below 20 o/o, have conventional
melting temperatures noticeably lower than those
the considered domainand at constant CaO content, the
observed with poorer ores (containing higher Si02) for
conventional melting temperature increases with the silica
the sameCaOcontent.
content. It meansthat the substitution of iron oxide by
silica in this part of the ternary system increases the
Figure 6
presents the calculated versus the observed
melting temperature. Onecan deduct from these experi-
temperatures for all the experiments. It can thus be said
that Eqs. (1) to (5) established in this study allow
ments that an increase of the basicity ratio of a sinter a good
prediction of the conventional melting temperature of
mix does not necessarily lead to a lowering of the melting
the adhering layer of sintering granules, which is
temperature. The conventional melting temperature is
important for the optimisation of the chemical
1353'C for an adhering layer with 150/0 CaOand 5olo compo-
sition of the adhering layer,
Si02 (CaO/Si02=3'O) and 1405'C for 120/0 CaOand
3o/o Si02 (CaO/Si02 =4.0). Consequently, it is more 3. Reactions between Slag and Nuclei
difficult to produce good quality sinters richer in iron as,
in spite of the basicity ratio increase, the lower
CaO 3.1. Experimental Method
content in the adhering layer makesit more refractory. Manyexperiments have already been developed to
This fact has led to the development of the binary sinter reproduce at a laboratory scale the iron ore sintering
mixes mentioned at the introduction of this paper.1 ~6) conditions.7,12 ~21) The main characteristics of someof
The improved CaOsegregation obtained in that way them are presented in Table 2. For this study, a new
allows the slag formation at lower temperatures for the apparatus was developed to reproduce conditions closer
sameglobal chemical composition. To produce goodiron to the industrial process. It consists of a vertical tubular
ore sinter with a single sintering mix, a reasonable CaO furnace heated by electrical heating elements. Thesample

C 1995 ISIJ 140

 ISIJ internationa], Vol, 35 (1 995), No. 2
Table 2. Main features of somelaboratory sintering tests.

Reference 13 14 15 17 19 20 This study

Sampleweight (g) 5 15 ? 1.2 0.4 ? 30/50

Sampledimensions d= 25 d= 15 d
= 20 d= ? d= 6 d= 19 N=2to 3
(mm) h=? h=10 h=2 h=? h=6 h=? A 5
Temperature range 1100 l 200 l OOO l 140 1180 l 100 1200
('C) 1350 1350 l 370 1390 1255 1400 l 350
Atmosphere argon ai
r arr arr, 1 CO
olo
arr alr
+0.50/0 coke Coc02 24 o/o C02 +0.80/0 coke
75 o/o N2
Time (s) 600 600 1200 TP 120 to 240 * TP
Analyses OM XR-EP OM OM EP ST OM-EP-IA
N= nucleus size. A adhering layer
= size.

= lO"C/s, time at maximumtemperature = 80 s.

heating rate 1
*:

TP= temperature profile similar to that existing in sintering, OM= optical microscopy, XR= X-ray diffraction, EP= electron probe microanalysis,
IA image analysis, ST "shatter-test".
= =
isput in a crucible (a truncated stainless steel cone) to Table 3. Chemical composition of the nuclei (2.(~2.5mm
be introduced in the furnace. To improve the coke fraction).

combustion in the sample, the crucible is provided with

several holes.
Fet Si02 Al203 CaO MgO P L.0.1.
o/o o/. o/o ~/o o/o olo o/o
In the industry, the amount of fuel simultaneously
determines the atmosphereand the thermal profile during Ore B 69.6 0,38 0.28 0.01 0.05 0,01 o.4
the process. However, in the laboratory experiments, the Ore E 64,3 4.67 0,67 0.01 0,05 0,06 3.7

atmosphereand the thermal profile are controlled almost Ore H 58.3 4,67 2.39 O, 14 O, 16 0.03 9.9

independently: the electrical resistances are the most

important source of heat and there is no suction. Fuel
addition tests were thus performed to obtain an inside the furnace that
was preheated at 1300'C. The
atmosphere close to the one existing in the industrial residence time at temperatures above 200'C measured 1
process. The aim was to find a coke level providing the in the sample 1
was 80 sec. After the heat treatment a few
experimental sinter a Fe2+ content close to that existing cracks in the grains of ore B, the transformation of
in an industrial one. The polynomial equation adjusted goethite into hematite and
manysmall pores in ore E
to the results is: and large fissures in ore were observed by meansof H
optical microscopy (see Fig. 7).
Fe2+ o/o (coke + 4.82 1 (coke olo)2
= 3.02 + 0.306 • o/o) •

The samples were submitted to mercury intrusion

(r=0.99, n=6) ........
..........(6)
porosimetry before and after heat treatment, aiming at
This meansthat in these laboratory experiments, to the evaluation of the structural changes. The choice of
this technique
produce a sinter with 25 o/o magnetite, which corresponds was due to the size of the iron ore grains
to about 6.4 o/o Fe2+, 0.8 o/o coke must be added to the and of their pores. It measures the pore diameters be-
raw mix. Such quantity corresponds approximately to tween 0.0075 and 15 ,lm; the pores above 15 pmhaving
that found by Matsuno and Harada,14) under similar little influence on the total specific surface of the nuclei
conditions (see Table 2). which will react with the slag. The distribution of the
porous volumes and the specific surfaces of the ores are
3.2. Experiments with Nuclei given in Table 4. It is worth noting that the specific
The iron ore grains corresponding to the nuclei were surfaces of all the three ores were reduced by the heat
first tested. They were submitted to
a heat treatment treatment, but the specific surface of the ore after heat H
aiming at the determination of their structural modifi- treatment was ten times bigger than that of ore B and
cations before reacting with the slag, No coke was four times than that of ore E.
added. The structure modifications were caused mainly Annealing produced a strong decrease of pores
by the dehydration and by the annealing of the grains, between O.OI and O, I ~m, while more complex combined
taking place respectively at about 300'C and at more effects of annealing and dehydration took place for the
than 1200'C.22) Thechoice of the iron ores used in these greatest pore diameters. For higher hydration values, the
experiments was based on the idea that the most im- formation of pores above I ktm is observed and, in the
portant characteristic with respect to the heating is the case of the ore H, almost pure goethite, even above
hydration degree of the ore. Consequently, the ores B 0,1 ~m. Because hydrated ores present greater
porous
(almost pure hematite), E(rich in hematite with goethite volumes after heat treatment, their nuclei are more
cementations) and H (massive goethite) were chosen. reactive. Onthe contrary, the nuclei of ore
Bcontained
After wet screening, the 2.0-2.5 fraction of the ores less porosity after heat treatment and would consequently
presented the chemical compositions given in Table 3.
mm better resist to the slag attack during the sintering process,
For each experiment, the crucible wasloaded with 50 g resulting in a higher primary hematite amount in the
of the 2.0-2.5mm fraction of each iron ore and placed sinter.

141 C 1995 ISIJ

 ISIJ International, Vol. 35 (1995), No. 2

Fig. 7.
Ore B before heat treatment (a) presenting hematite
(H) and after heat treatment (b) presenting hematite
(H) and fissure (F); ore E before heat treatment (c)
presenting hematite (H) plus goethite (Goe) and after
heat treatment (d) presenting hematite (H) and hematite
plus fine pores (H1) formed from goethite; ore
H before
heat treatment (e) presenting massive goethite (Goe) and
after heat treatment (O presenting hematite plus fine
pores
formed from goethite (H1) and large cracks.

Table 4. Porous volume distribution and specific volume of the heat treated (HT) nuclei.

Partial volume Global volume Specific surface

Pores size:
0.01 to 0.1 0.1 to 1.0pm 1.0 to 15.0,lm
~m 0.01 to 15,4m
3•g~1
mm 3.g~1
mm 3.g~1
mm 3•g~1
mm m2'g -l
Ore Bbefore HT 2 5 13 20 0.32
Ore Bafter HT o 2 ll 13 0.03
Ore Ebefore HT 6 7 17
Ore Eafter HT
30 1.OO
o 5 22 27 0.09
Ore H before HT 11
9 5 25 1.27
Ore H after HT 2 ll 15 28 0.34

3.3. Experiments with Granules particles are given in Table I while those of the nuclei
This part of the study deals with the effects of the iron are in Table 3.

ore structure and of the thermal profile on the reactions The raw materials were mixed to produce sinters with
between slag and nuclei. The nuclei (iron ore grains a basicity index (CaO/Si02) of 2.1 and silica content
between2and 2.5 mm)were those studied in the previous between 4 and 5o/o. The limestone and burnt lime ad-
part. The fraction below O.5 (obtained by screening) ditions were kept constant at 10 and 3o/o, respectively.
added to reconstitute the
mmproportion between nu- The basicity index was adjusted by sand addition. In the
was
clei and adhering particles of each iron ore. The ore case of iron ore H, which is the richest in silica, no sand
concentrate D(in a 25 : 75 ratio to the base ore) wasused was added to the raw mix. The calculated chemical
in all mixes. The purpose of this addition compositions of the adhering layers after calcination
was to
reproduce the present trend of using finer ores in the are presented in Table 5, while the calculated chemical
sinter mix. The chemical compositions of the adhering compositions of the laboratory sinters are presented in

C 1995 ISIJ 142

 ISIJ International, Vol. 35 (1 995), No. 2
Table 6. The iron contents of the adhering layers were MASSIVE
FERRITES
lower than in the sinters and their basicity indices higher 1oo GANGUE
ANDVITREOUS
PMASES
(ranging from CaO/Si02=2.2 to 4.3) than that of the FERRITES
TABULAR
~'~~CICVLARFERnITES
sinter (CaO/Si02 = 2. 1). 80
The residence time inside the furnace wasprogressive- ~~;oe MAeNETITE
ly augmentedto produce increasing slag amounts. The C 60
O
target values for maximum
temperature were distributed CJ
SECONDAnY
}IEMATITE

between 1200 and 1350'C, with 25'C steps. Twenty-one S,

C:, 40
experiments were carried out (7 maximum temperature (D

and 3different iron ores). The sinters were submitted to

optical microscopy observations, to quantitative phase 20 PRIMARY
HEMATITE

determination with an image analyser and to the electron

probe microanalysis of the calcium ferrites. o
1225 i 250 1275 1300 1325 1350
3.3.1. Phase Analysis and Morphology T max ('c)
a) Sinters B
Figure 8 shows the fitted
of mineral variations
phase composition versus maximum temperature in the 1oo eANGUE
ANOVITREOUS
PHASES
experiments, determined by image analysis. The results FERRIfES
MASSIVE

of the quantitative phase anaysis of the sinters produced TABULAR

FERRITES
80
at low (about 1250'C) and higher (about 1350'C) FERRITES
ACICULAR

temperatures are presented in Table 7. In all cases the o\e

M'LGNET
60 IrE
primary hematite amount diminished with increasing C
O SECONDARY
HF_M,\TITE
temperature. It was as first essentially replaced by O
CU
secondary hematite, and at temperatures higher than 40
C9

l 257'C, by magnetite. As predicted in Sec. 3.2, the nuclei a,

of ore B were less attacked by the slag. Consequently 20

the sinters madewith this ore had
moreprimary hematite HEMATITE
PRIMARY
than those with the two other ores. The total calcium o
ferrites (SFCA)content was maximum at the following 1225 1250 1275 1300 1325 1350
temperature: 24 o/o at 1225'C for ore B, 24 o/o at 1250'C T max ("c)
b} Sinters E

Table 5. Calculated chemical compositions of the adhering 1oo GANGUE

ANDVITREOUS
PHASES
layers after calcination. M/~SSlvEFEpnjTES

80
Fet
olo
Si02
olo
Al203 CaO MgO ;LCICULARFERRITES
TAEVLAR
FERRITES
"/o 'lo "/o ~~ee

C: 60
Sinter B 55.6 5.9 0.7 1~O 0.2 O
o
MAGNETITE
Sinter E 57.2 4.0 0.7 13.0 0.2 ro

Sinter H 53.4 3.9 l.8 16.8 0.2 ro

o
40

SECONDARY
HEMATITE
20
Table 6. Calculated chemical compositions of the labora-
tory sinters. FRIMARY
HEMATITE
o
Si02 CaO 1225 i 250 1275 i 300 1325 1350
Fet Al203 MgO
Qlo olo o/o ol* o/o T max("C)
c} Sinters H
Sinter B Fig. 8. Laboratory scale: phases distribution in function of
59.3 4.5 0.7 9.4 O.
l
Sinter E 58.9 4.6 o.9 9.6 O.
1 maximum
temperature (a) sinters B; (b) sinters E; (c)
Sinter H 57.4 4.8 2.2 1O. l 0.2 sinters H.

Table 7. Phase analyses of laboratory sinters produced at lower and higher temperature.

Tmax PH SH MAG SFCA AF TF MF GAN

oC Ol
lO
o/o o/o olo Ol
lO
o/o olo olo

Sinter B 1256 48.4 15.1 8.

1 20.6 12.l 5.5 3.0 7.8
Sinter E l 256 27.4 24.7 21.6 20 2 .
7.5 6.6 6.l 6.
l
Sinter H 1264 32.3 23.6 7.7 32.7 l 3.0 l 1.7 8.0 3.7
Sinter B l 347 27.1 27. l 29.6 9.0 2.5 4.3 2.2 7.2
Sinter E l 352 ll.7 34.7 29.3 17.8 5.9 9.0 2.9 6.5
Sinter H 1355 3.7 24.9 35.2 25.0 2.8 15,7 6.5 l I .2
PH= Primary Hematite, SH= Secondary Hematite, MAG
= Magnetite, SFCA
= Silico Ferrite of Calcium and Aluminium, comprehending:
AF=Acicular Ferrites. TF=Tabular Ferrites and MF=MassiveFerrites. GAN=Gangue
and vitreous phases.

143 C 1995 ISIJ

 ISIJ International, Vol. 35 (1 995), No. 2
Table 8. Microanalyses of SFCAproduced at lower and
higher temperatures in the laboratory experiments.

Tmax Ca Fe Si Al O
oC o/o olo o/o c/o olo

Sinter B l 256 9.7 57.6 l .6 0.9 30,2

Sinter E l 256 9.5 59.2 0.7 0.6 30,0
Sinter H 1264 l O, l 56.8 1.6 l.l 30,4
Sinter B l 347 6.6 63.6 0.6 0.6 28.6
Sinter E l 352 l0.9 58.4 0.6 l.1 29.0
Sinter H l 355 8.6 58.2 1 .2 l.5 30.5

Table 9. Calculated chemical compositions of the adhering

layers of the laboratory sinters.

Ca Fe Si Al O
olo o/o olo o/o o/o

Mix B 9.3 55.6 2.8 0.4 31.9

Mix E 9.3 57.2 1.9 0.4 31.2
Mix H 12.0 53.4 1.8 1.O 31.8

3.3.2. Electron Probe Microanalyses of SFCA

The of the electron probe microanalyses of
results
SFCA produced at lower and higher maximum tem-
peratures are presented in Table and the calculated 8
chemical compositions of the adhering layers are
Fig. 9. (a) Sinter structureformed at lower temperatures (mix presented in Table 9. These tables show that at lower
B) presenting acicular ferrites (CF), gangue (G) and temperatures the chemical compositions of SFCA
primary hematite (PH); (b) sinter structure formed at
were
similar to those of the adhering layers that generated
higher temperatures (mix H) presenting massive SFCA
(CF), secondary hematite (SH) and vitreous phases them, with two exceptions. Firstly, the alumina contents
(VP) .
were always higher in the SFCAthan in the adhering
layer. Secondly, in the experiments with ores and E, B
with quartz addition, the SFCA presented silica contents
for ore E and 35'/o at 1300'C for ore H. At higher
lower than those of their adhering layers. The optical
temperatures the SFCAamount diminished mainly in
favour of magnetite and, in a lesser extent, of vitreous
microscopy confirms that in these two cases the quartz
in the adhering layer (predominantly from the sand
phases. The sinter mix with ore H
generated the largest
addition) did not react thoroughly. At higher tempera-
SFCAamounts, mainly of the tabular type. The higher
tures, that similitude was not so evident, probably due
alumina content,23,24) the higher basicity and the higher
to the partial reaction of the slag with the nuclei.
gangue volume of the adhering layer of the granules
made with ore H
were the causes of more intense 4. Pilot Plant Experiments
formation of SFCA. Acicular SFCAwere obtained
essentially at lower temperatures. The morphology of The previous part of this study has shown that the
the massive SFCAchanged strongly as a function of mineral phase composition of iron ore sinters can be
the temperature. At lower temperatures, under 1250'C, adjusted by varying raw mix and heat pattern. On the
they consisted predominantly of precipitations at the other hand, the mineral phase composition determines
periphery of the iron ore nuclei or burnt lime (from the sinter properties. To check this, experiments with three
calcination of limestone grains) forming SFCAag- of the previously tested ores were carried out at a pilot
gregates that were classified as massive. At higher plant.
temperatures well-defined massive SFCA crystals, asso-
4.1. Experimental Method
ciated with secondary iron oxides and vitreous phases,
The sinter mix is prepared according to a standardised
were progressively precipitated form the melt. The
procedure. It is then weighed and loaded in the sinter
amount of gangue plus vitreous phases did not vary
noticeably in function of the maximum pot, which consists of a steel cyiinder with 330mm
temperature and
internal diameter. In this study, the bed height wasfixed
they were classified together in this study. Upto 1280'C,
at 400 mm.The ignition of the sinter mix fuel is made
one could observe predominantly ganguefrom the sinter
mix that did not react (Fig. 9a) At higher temperatures, by meansof a furnace movedonto the pot. The sintering
increasing amountsof vitreous phases precipiiated from
is carried
on with a suction head of 147 hPa. After
the liquid cooling, the sinter cake is stabilised, sieved and the
as the original mineral matter dissolved (Fig.
fraction below 5.6 constitutes the return fines.
9b) mmthe
average of two experiments
.
The test results are

C 1995 ISIJ 144

 ISIJ International, Vol. 35 (1995), No. 2
that must meet the following tolerances: others). The return
two fines were produced in prelimi-
nary test with the samemix and at the samesintering
+1010
cold permeability conditions. The productivity, fuel specific consumption
+5010
sintering
....,.............................
speed ...................................... _ and Fe2+ content obtained at each sintering test are also
+30/0
sinter cake weight ................................. +1010
presented in Table 1 3 .

return fines balance ...............................

Thesinter with ore Bdemanded less fuel to be produced
+ 0.05 because of the compact nature of the hematite nuclei of
specific production
................................ + 2.5 olo its sinter mix granules. It presented the highest
primary
cohesion index (ISO T) +1olo
4.2. Results
.........................
_ hematite content (26 "lo). Ore demanded
more fuel than H
ore B, needed for the dehydration of the goethite and
The data corresponding to this series of experiments the formation of a higher matrix (SFCAand vitreous
are given in Tables 10 to 14. The return fines input was phases) content (50 o/.). In this case, fuel
was also
aimed at 20 o/o of the mix, as it corresponds to the demandedto diminish the content of its very porous,
industrial practice. To achieve the equilibrium of return unsound, primary hematite produced from the goethite.
fines, the fuel addition
was adjusted, as shownin Table The sinter produced with ore E required the samefuel
13 (3.6 o/o fixed carbon for the mix and 4.5 o/o for the B amount as with ore H
because the porosity resulting
from the goethite dehydration must be drastically
reduced. In this case the primary hematite is replaced
Table lO. Chemical analyses of iron ores and additions in
the pilot plant.
essentially by magnetite (340/~ of the sinter).
The sinter mineralogy obtained in the pilot plant trials
Fet Fe2+ CaO Si02 MgOAl203 P L.0,1. is therefore in good
agreement with the results obtained
olo o/o o/o olo olo o/o o/o o/o
in the laboratory experiments, presented in Table
7and
discussed in Sec. 3.3. I The observations madeby
Ore B 68.5 0.17 0.69 0.05 0.43 0.03 0.5 . means
Ore D of an optical microscope confirmed that the acicular
66.7 o.2 0.09 l .98 0,03 0.77 0.0 l l .O
Ore E 64.8 o.9 0.04 4.46 0.04 O.81 0.09 2.6 SFCAare usually associated with fine porosity and
Ore H 56.8 O.
l 0.28 5.57 O.12 2.59 o,03 8.5 primary hematite (Fig. 10). This is the heterogeneous or
Limestone 0.2 NA 54.50 0.62 0.94 0.20 NA 42.9
two-components sinter structure, proposed by Vidal et
Burnt lime 0.2 NA 94.8 0.32 NA 0.15 NA 2.8 al.,25) which gives the best sinter properties.
Sand 0.7 NA 0,21 95.01 NA 2.80 NA 0.6

Table 13. Process and quality variables in the pilot plant.

Table 11. Grain size distribution of raw materials in the
pilot plant. Experiment Sinter B Sinter E Sinter H
l 0-20 5-lO , 15-5 23. 15 12 0.5-l O~).5
MD Mix moisture (o/.) 5.8 7.3 7.8
o/. o/o o/o o/o o/. o/o Fixed carbon (o/o)
olo
mm Return fines input ("lo)
3.6 4.5 4.5
20 20 20
Ore B O.3 l0.3 14.1 13.9 l 3.4 12.3 35.7 2,
IO Sintering speed (mmmin ~ 1) ' 26 23 21
Ore D O.
1 O.3 99.3 0.04 Maximum
Ore E
temperature ('C) l 308 l 357 1355
1.9 13.4 9.6 8.2 8.8 5.
1 53.0 2.
12 Retungfines balance (out/in, in weight) 1.02 1.OO 1.OO
Ore H 2.7 27.4 13,6 11.O ll.6 9.
l 24.6 3.59 Productivity (t ~ 2 day~ 1)
Limestone 0.4 9.4 31.0 22.4 36.8 0,88
•

m ,

Fuel specific consumption (kg/t sinter)

52.6 44.6 34.0

Burnt lime
47.9 61.6 64.4

Sand
l OO ND
O,6 3,4 7.9 21.8 66.3 0,56 Sinter porosity (mm3g~ 1) ' 8.
l 7.4 10.7
Fe2+ (./*) 3.6 6.4 5.4
MD:mediumdiameter. ISO 3271 T ('/.) 72.6 68.9 63,3
ISO 3271 A ('/.) 5.0 5.3 6.4
Table 12. Mixes and chemical composition of sinters in the ISO 4696 ("/. > 3. 15mm) 75.9 67.5 39.8
pilot plant.
Reducibility ('/.) 65.3 62.0 67.3

Mixl Mix B Mix E Mix H

Components ol. o/. o/o Table 14. Mineralogical composition of the sinters pro-
duced in the pilot plant.
Ore B 62.0
Ore D 20.7 21.3 21.5
Ore E
Sinter B Sinter E Sinter H
64.0 o/o olo olo
Ore H 64.5
Limestone 11.0 l I .O 11.O Primary hematite 26 4 4
Burnt lime 3.0 3.0 3.0 Secondary hematite 23 24 26
Sand 3.3 O.7 Magnetite 15 34 20
Gangueand vitreous phases 9 14 8
Fe* 59.3 59.4 57.4 SFCA(total) 27 24 42
CaO 9.4 9.6 10.
1
Si02 4.5 4.6 4.8 Acicular SFCA 8.8 7.1 7.6
MgO O.
1 O.
1 0.2 Tabular SFCA 13.8 14.7 22.3
Al203 O.7 0.9 2.2 Massive SFCA 4.4 2.2 12. 1

145 C 1995 ISIJ

 ISIJ International, Vol. 35 (1995), No. 2
Matsunoet al.,29) small pores surrounding the secondary
hematite hinder the propagation of the fissures formed
in that phase during the hot degradation process.
The hot degradation tests were carried out according
to the ISOStandard 4696. After test, the 3. 15 oversize
is defined
as hot strength index. The hot
mm
strength of the
sinter produced with the ore
H is rather
poor, only 39.8.
The examination with the microscope shows that the
secondary hematite is immersedin a vitreous matrix or
associated with massive SFCA,as in Fig. 9b. In this case,
the fissure propagation occurs more easily. The sinter
madewith ore B presented a total amount of massive
SFCAand vitreous phases sensibly less important than
the two others, as in Fig. 9a, mainly because of the lower
Fig, lO, Structure oftwo-componentsinter(mixB): heat input required for its production. Consequently, this
two nuclei
of primary hematite (PH) bonded by a structure sinter has the best hot strength index, 75.9 (see Tables
composedmainly of SFCA(CF) and a mixture of 13 and 14). One can also assume that the lower cold
very fine primary and secondary hematite (H). strength of the sinter madewith ore Hhad a negative
influence on its hot strength.
4.2.1. Sinter Cold Strength 4.2.3. Sinter Reducibility
Sinter cold strength is characterised, according to the In this work the sinter reducibility was characterised
ISO standard 3271, by the cohesion index (ISO T, by the weight loss measured after a reduction test,
fraction above 6.3mmafter (test) and by the abrasion performed in the following conditions:
index (ISO A, fraction below 0.5 after test). The low
mm
resistant vitreous phases (in someextent, also SFCA),big - sample: 450g, 10 to 12mm
(50~lo);
(500/0) and 12 to 15mm

cracks and big pores hinder sinter cold strength.26-28)
Usually, a higher amountof coke breeze is employed to
improve the cohesion strength by reducing the porosity.
Nevertheless, the production costs and the diminution
of sinter reducibility lead the producers to choose ores
and sinter mix compositions that permit them to reduce
the formation of vitreous phases, big pores and cracks,
even whendiminishing coke breeze consumption.
Table 13
indicates that the sinter produced with the
hematite ore B
has the highest cohesion index (ISO
T=72.6), while the sinter produced with the goethite
ore H has the lowest index (ISO T= 63.3). The inter-
mediary value obtained by the sinter madewith ore E
(ISO T=68.9) corresponds to the intermediary nature
of this ore: hematite with cementations of goethite. Table
14 shows that the sinter produced with ore H has more
matrix (SFCAplus vitreous phases) than the two others
(50 o/o against 35 "/o). The increased quantities
preheating up to I OOO'Cunder N2 fiow;
at I OOO'C during I h, gas flow of Nm3/h,
- reduction I
40 "/o COand 60 "/, N2'
This test reproduces approximately the conditions
existing in the indirect reduction zone of the blast furnace.
The reducibility index gives the percentage of oxygen
associated with the iron oxides of the sample that is
removedduring the test. It is well knownthat the sinter
ought to be well reduced before it reaches the zone of
direct reduction. A better sinter reducibility corresponds,
in someextent, to a lower coke-rate in the blast furance.
Sinter reducibility is frequently related to the open
porosity and the results shown in Table 13 obey the
expected trend: the sinter madewith ore H presented a
reducibility of 67.30/0 and a porosity of 10.7mm3 'g~ l
followed by the sinter madewith ore B, with respectively
65.30/0 and 8.1 mm3'g~1and, at last, the sinter made
of matrix, with ore E, with 62.0"/. and 7.4 mm3g~ 1. This positive
'

fissures and macropores of the produced with ore

sinter effect of sinter porosity
on its reducibility has been stated
H explain its lower coldits strength. The highest primary by someauthors.22,27,30)
hematite content and compact nature in the sinter
madewith ore Bare at the origin of the higher cohesion 5. Conclusions
index.
In this work the sinter mineral phase composition was
4.2.2. Sinter Hot Strength optimised by meansof the adjustment of the adhering
The main source of during the sinter reduction
fissures layer chemical composition and by the choice of the iron
in the blast furnace the secondary hematite that
is
step, Iaboratory
ore nucleus mineralogy. In a first
contains fewer pores and more aluminium than the experiments were carried out with pulverised iron ores
primary hematite (the aluminium distorts the hematite and additions. They showed that the silica additions
lattice). According to Loo et al.,28) the propagation of between 5 and 15'/o Si02 augmentedthe conventional
the fissures is inversely related to the toughness of each melting ternperature at any CaOcontent between 10 and
mineral phase. The phases with the lowest toughness, 20 o/* CaO. Consequently, the richer iron ores required
i.e. massive SFCAand vitreous phases, are primarily less CaOaddition than the poorer ores to reach the same
responsible for the propagation of fissures. Therefore, conventional melting temperature.
lower contents of secondary hematite, massive calcium In a second step, experiments in a laboratory furnace
ferrites and
gangueimprove the sinter hot strength. After designed for this study showedthat, in function of their

C 1995 iSIJ 146

 ISIJ International. Vol. 35 (1 995), No. 2
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CNPq(Brazil) and CRMfor supporting this work.

147 C 1995 JSIJ