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experimental investigation on high temperature roasting of

basic oxygen furnace slag


Ruirui Wei, Meilong Hu, Fangqing Yin, Yanhui Liu College of Materials
Science and Engineering, Chongqing University, China
Keywords: BOF slag, roasting, SFCA, sintering.
RESUMEN
In China, Basic Oxygen Furnace (BOF) slag is traditionally used as an
aggregate for civil engineering, for road engineering and fertilizer. In
order to make full use of BOF slag, the experiments of BOF slag with
high temperature roasting has been carried out and the phase
transformation is studied. The BOF slag from Chongqing Iron & Steel
is roasted in the electric muffle furnace at three different
temperature. The influences of the high temperature roasting on
change the phase composition of BOF slag was characterized by XRD.
The results revealed that SFCA was produced at the high temperature
in air atmosphere and melting temperature of slag was lowered.
Therefore, if the BOF slag which treated by roasting was utilized in the
sintering process, it is advantageous to improve the sintering strength
and the formation of the liquid phase and reduce fuel consumption in
the sintering production process.
INTRODUCCIN
Since the beginning of the industrial era, slags, which have been
considered waste production, started appeared as a major by-product
obtained during the extraction of metals from ores through
metallurgical processes. According to the report of the World Steel
Association, there are about 1580 million tons crude steel output
around the world in 2013, and the crude steel output of China
accounts for almost 49.2wt% of the global crude steel output. During
the process of steel production in Basic Oxygen Furnace (BOF), for
every ton of crude steel, about 100-150 kg of slag is generated in the
form of waste[l]. Therefore, nearly 77.9-117 million tons BOF slag is
being generated as a solid waste and this figure will increase in future
years [2]. This is a huge figure so that researchers are looking for an
efficient and environmental way to utilize BOF slag. At present, some
of the slag is recycled to the blast furnace [3-5] while a significant
portion is used in civil engineering application, such as cement and
concrete [6-8], due to its superior skid and wear resistance [9].
However, the latter utilization of BOF slag has some restrictions in
many regions owing to an undesirable expansion of the slag
aggregate [10] leading to rapid deterioration of the roads. The volume

expansion (up to 10%) is attributed to the short and long term


hydration of the calcium and magnesium oxides content, especially
free lime [10-14].

According to the composition of BOF slag, over half of it is made up of


CaO and iron oxides, using this slag for land filling and road ballast
does not justice to its potential value. Steel enterprises all the world
face a same challenge in treating this under the prevailing
environmental regulations. Therefore, researchers in different parts of
world are looking for an efficient method to utilize BOF slag.
Normally, CaO occurs in BOF slag as 2Ca0-Si02, 3Ca0-Si02 and low
melting point minerals [15-17], Consequently, by the addition of
certain percentage BOF slag is beneficial to form liquid phase,
improve quality and strength of sinter ore and decease fuel
consumption in sintering process [18]. In addition, BOF slag can
replace part of sintered flux to ensuring comprehensive utilization and
recycling of resources.
In the present study, to form more SFCA in BOF slag, the experiments
of BOF slag from Chongqing Iron & Steel with high temperature
roasting has been carried out and the phase transformation is
investigated as part of a large project on the recycling of BOF waste
slag. Results obtained from the present study provide some
fundamental information for the utilization of BOF slag in the sintering
process.
experimental
An industrial sample of BOF slag, come from Chongqing Iron & Steel is
used for the experiments. The quantitative analysis and the chemical
composition of the BOF slag, as measured by using X-ray fluorescence
spectrometer (XRF-1800, SHIMADZU, Japan), were summarized in
Table I [ 19]. The contents of TFe, Fe 2+, and Fe3+ in the BOF slag were
also determined by chemical analysis. From Table l,CaO, MgO and
Si02account for about two thirds of slag. And the phase identification
of BOF slag was determined by X-ray diffraction as Fig.l. The main
phase of slag were Ca2SiO4, (Ca,Fe,Mg)3Si05, CaO, Ca2Fe2O5 and Fe3O4.

Table I. Main composition of BOF slag, %


Compositi
SiO Al2O Mn
CaO MgO
TFe
P
on
2
3
O
Content,wt 40.2
14.6
2.5 18.4 0.7
8.19
2.40
%
1
9
4
4
5

S
0.1
3

Fig.l. XRD pattern of the BOF slag.


The BOF slag was ground into 200 mesh with mill machine and place
it into oven at 120C for 2 hours. The thermal analysis (TA)
measurements were carried out using a NETZSCH STA 449C TG-DSC
instrument, at a heating rate of 10C min -1 to heat to 1350C in air
atmosphere.
Subsequently, the BOF slag of 20g was placed in an alumina plate and
roasted in an electric muffle furnace with automatic temperature
control and the roasting process is prohibited in the temperature
range of 800~1000C, the process was as follows: 1) heating the slag
to roasting temperature at 0.5h, 2) keeping the roasting temperature
for 1h and stirring slag once, 3) Cooling with the furnace and taking it
out when cooled to 150C.
The adding weight during roasting experiments was calculated by
measuring the change in weight of the samples before and after the
roasting process, and phase identification of samples was determined
by X-ray diffraction (D/MAX 3C, RIGAKU company, Japan). In the end,
The hemisphere method was adopted to measure the melting
temperature,
including
softening
temperature,
hemisphere
temperature and flow temperature of slag unroasted and roasted at
1000 C.
results and discussion
Thermal analysis experiment
Some changes in weight, thermal activities were observed during TA
experiments.Fig.2 represents a TG-DSC diagram obtained by heating
BOF slag sample in air atmosphere.

Fig.2. TG-DSC curve for BOF slag in air.


The TG curve in Fig. 2 shows two distinct stages of mass loss at
200~420C and 580~690C, accompanied by endothermic reaction
on the DSC curve. A gradual mass gain between 690C to 1060C was
also observed. The first stage is typical of dehydration of crystal water
and the dehydroxylation of Mg(OFl)2. And the second stage is typical
of the dehydroxylation of Ca(OH)2 and the decomposition of CaC0 3,
absorbing much heat, according to the following reactions:

The main gain between 690C to 1060C is due to the oxidation of


iron and iron oxidation in the sample, which can be verified by the
subsequent detection of X-ray diffraction. Two small endothermic peak
can be observed in Fig.2 thanks to generation of new phase, such as
Ca2(Fe,Al,Mg,Si)O5,
Ca3(Al,Fe)(SiO4)3,
(Ca,Fe)(Al,Fe)(SiO4)3
and
Ca5Si2(Fe,Al)18O36, which can be regarded as the different molecular
formula of SFCA. In addition, from the tiny exothermic peak range
from 840C to 1310C, it indicated that substitution reactions among
cation in slag occurred, part of Fe 3+ was replaced by Si4+, Mg2+ and
Al3+ and crystal structure of compounds was changed [20].

Roasting experiments of BOF slag


The weight change of BOF slag roasting at 800-1000C was showed in
Fig.3. It was clear that weight gain rate decreased when roasting
temperature was 800C.This is because the thermal decomposition of
calcium carbonate produces calcium oxide and carbon dioxide and
dihydroxylation of calcium hydroxide and magnesium hydroxide. And
then, weight gain rate increased due to the oxidization of iron and
iron oxidation with a rise of temperature in air atmosphere. By and
large, following the increase of roasting temperature, the mass gain
rate increases, implying more iron and iron oxidation are oxidized, and
maintain a growing tendency, but mass gain tends to unchanged after
1000C. The reaction was shown as following equations 3.4-3.8:

Fig.3. Weight change curve of roasting slag.

Fig.4 shows the XRD patterns of the three samples roasted in air
under 800-1000C. In this figure, it is obvious that the main phase of
roasting slag range from 800C to 1000C are Ca 2(Fe,Al,Mg,Si)O5,
Ca3(Al,Fe)(SiO4)3, (Ca,Fe)(Al,Fe)(SiO4)3, and Ca5Si2(FeAl)18O36, which is

considered of different forms of SFCA. The substitution reactions were


further verified by foregoing phase of roasting slag. The ion
replacement mechanism of SFCA can be understood as the following
reactions:

Fig.4. XRD patterns of the samples roasted in air.


The slag unroasted and roasted at 1000C was used to measure the
melting temperature with hemisphere method, and the result in Table
II showed that lowering of melting point through roasting the slag in
the air was preferably well. When roasting the slag lh at 1000C, the
softening temperature of slag was decreased from 1350 C to 1344
C, hemisphere temperature from 1363Cto 1358C, and flow
temperature from 1372 C to 1356 C. This should be attributed to
the generation of SFCA after roasting. And it means that roasting the
slag help decrease the melting point of slag so that it can be reduce
the consumption of power and energy and improve quality and
strength of sinter ore if available in sintering process.

Table II. Melting temperature of BOF slag


Roasted slag at
BOF slag
Unroasted slag, C
1000C,C
softening
1350
1344
temperature
hemisphere
1363
1358
temperature
flow temperature
1372
1356
CONCLUSIONES
The feasibility of BOF slag into a useful sintered flux by roasting at
high temperature has been demonstrated.
(1) The BOF slag was roasted range from 800C to 1000C in air,
mass gain increased with the increase of temperature due to more
iron and iron oxidation were oxidized, and mass gain tended to
unchanged after 1000C. According to the XRD patterns of roasted
slag, the phase of SFCA was observed. This means that roasting the
BOF slag help the generation of SFCA.
(2) The experience of measuring the melting temperature of BOF slag
unroasted and roasted at high temperature with hemisphere method
has been carried out. The result shown that roasting the BOF slag at
high temperature facilitated to lower the melting temperature.
(3) According to the present study, in the roasting slag at high
temperature, the slag shows excellent phase composition and
properties, observing the SFCA and lowering melting temperature of
slag. The generation of SFCA is propitious to form more liquid phase
easily, improve quality and strength of sinter ore in sintering process.
And lowering the melting temperature of slag can decrease fuel
consumption to save more energy during sintering process. Moreover,
roasting slag can replace part of sintered flux to ensuring
comprehensive utilization and recycling of resources.
Acknowledgements

This work was supported by "the Fundamental Research Funds for the
Central Universities" (Grant No. CDJZR14135501) and "Specialized
Research Fund for the Doctoral Program of Higher Education" (Grant
No. 20130191110015).
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