Technical Field
[0001] The present invention relates to an agglomerated ore assessing method for assessing
clustering of agglomerated ore, and to agglomerated ore.
Background Art
[0002] Global warming due to increasing CO
2 has been widely taken up as an international issue, and reducing CO
2 emissions has become a challenge facing the entire world. Of about 1.9 billion tons
of crude steel produced worldwide, about 1.4 billion tons are produced by a blast
furnace-converter method. Because coal is used in the blast furnace-converter method,
as large an amount of CO
2 as 2t-CO
2/t-Fe is emitted. The remaining 0.5 billion tons or so are produced by a method other
than the blast furnace-converter method: a direct-reduction process. A shaft furnace
solid reduction + electric furnace method represented by MIDREX
® that accounts for 60% or more of the direct-reduction process can reduce CO
2 emissions to about 1.1 to 1.2 t-CO
2/t-Fe. To reduce CO
2 emissions from the iron industry, it is necessary to shift from the blast furnace-converter
method to the direct-reduction process, and further to increase the ratio of hydrogen
reduction.
[0003] Raw materials used in the direct-reduction process tend to be of high iron grade
compared with those in the blast furnace-converter method. In particular, for reduction
in a shaft furnace, pellets of uniform particle size are used as the raw material
to secure gas permeability inside the furnace. It is known that, when reduction progresses
and the raw material descends down the furnace, clustering occurs in which reduced
iron particles adhere to one another under the load of the raw material accumulated
at a high-temperature area in front of a tuyere at a lower part of the shaft furnace.
Occurrence of clustering is problematic because it prevents the reduced iron from
being discharged from the shaft furnace. To prevent clustering, it is important to
manage the properties of the raw material charged into the shaft furnace.
[0004] To what extent an agglomerated raw material adheres during reduction has been hitherto
assessed by the MIDREX hot load test described in Non-Patent Literature 1. According
to Non-Patent Literature 1, 2000 g of a sample is charged into a furnace, where it
is reduced to a degree of reduction of 95% in an isothermal environment of 850°C with
a gas composed of 45% H
2 + 30% CO + 15% CO
2 + 10% N
2 flowing at 40L/min. Sixty minutes after the start of reduction, a load of 147 kPa
is applied to the surface of the charged bed of the sample. After cooling, a cluster
formed during reduction is rotated ten times by a one-meter tumbler test machine,
and then the ratio of particles 25 mm and over, which are defined as a cluster, is
assessed as a cluster index.
Citation List
Non-Patent Literature
Summary of Invention
Technical Problem
[0006] The cluster assessing method described in Non-Patent Literature 1, in which the gas
contains CO and CO
2, cannot sufficiently assess the aggregability of a charged material when it has been
reduced with pure hydrogen. This method may fail to assess disintegratability in the
case where clustering of a material charged in a furnace is intensified as reduction
is completed earlier and yields a larger amount of metallic iron due to a higher reaction
rate of hydrogen reduction. When gas components include CO and CO
2, reduced iron becomes carburized and less prone to clustering (FIG. 6 of Non-Patent
Literature 2). With clustering thus reduced, the conventional assessment method may
fail to accurately assess a clustering phenomenon inside a hydrogen-reduction shaft
furnace.
[0007] In reduction of iron oxide, CO reduction is an exothermal reaction, whereas H
2 reduction is an endothermal reaction. Therefore, when CO reduction is reduced and
the ratio of H
2 reduction is increased, thermal compensation in the system becomes necessary. One
possible way of this thermal compensation is to increase the blowing temperature and
the blowing flow rate. In this case, in front of the tuyere, particles for which reduction
has been completed would be present, and particles of which the particle temperature
has been raised to near the temperature of the blown gas would be present. Thus, at
the point of 95% reduction in the conventional method, clustering is less likely to
occur due to the reduced particle temperature as a result of heat absorption during
hydrogen reduction, and to the low test temperature of 850°C. For this reason, the
conventional assessment method may fail to accurately assess clustering inside a hydrogen-reduction
shaft furnace in the case where the ratio of H
2 reduction is high and thermal compensation is made using blowing sensible heat.
[0008] The present invention has been devised in view of these circumstances, and an object
thereof is to provide an agglomerated ore assessing method that can assess clustering
of reduced iron when it has been reduced at a high hydrogen concentration, with thermal
compensation using blowing sensible heat taken into account, and to provide agglomerated
ore based on this assessing method.
Solution to Problem
[0009] The present invention is an agglomerated ore assessing method characterized in that:
agglomerated ore is reduced while being subjected to a predetermined load at 1000°C
to 1200°C, both inclusive, to produce a reduced aggregate; a tumble treatment is performed
on the reduced aggregate using a tumble tester; cluster strength CS of the reduced
aggregate calculated by Formula (1) below is measured; and a clustering property of
the agglomerated ore is assessed using the cluster strength CS:

where CS is cluster strength (mass%); W is the mass (g) of a reduced aggregate that
is equal to or larger than a maximum particle diameter of the agglomerated ore; and
W' is the mass (g) of a reduced aggregate after a tumble treatment in the tumble tester
that is equal to or larger than the maximum particle diameter of the agglomerated
ore.
[0010] In the agglomerated ore assessing method according to the present invention configured
as described above, the following are considered to be more preferable solutions:
- (1) that the reduced aggregate is produced using a reducing gas that does not contain
a compound having a C atom; and
- (2) that the reduced aggregate is produced using a reducing gas containing 70 vol%
or more H2.
[0011] Further, the present invention is agglomerated ore characterized in that cluster
strength CS
30 is 0 mass% as measured in the above-described agglomerated ore assessing method using
the reduced aggregate having been reduced at 1000°C and a reduced aggregate after
the tumble treatment obtained by rotating the reduced aggregate 30 times at 30 rpm.
[0012] In the agglomerated ore according to the present invention configured as described
above, the following are considered to be more preferable solutions:
- (1) that the particle diameter is 8 mm or larger;
- (2) that the total Fe is 64.5 mass% or less; and
- (3) that Formula (2) below is met:

where Al
2O
3 is the component concentration (mass%) of Al
2O
3 in the agglomerated ore, and SiO
2 is the component concentration (mass%) of SiO
2 in the agglomerated ore.
Advantageous Effects of Invention
[0013] According to the present invention configured as described above, an agglomerated
ore assessing method can be obtained that assesses clustering at a higher temperature
than the conventional method, and can thereby assess clustering of agglomerated ore
taking into account thermal compensation that is made using blowing sensible heat
in hydrogen reduction. Thus, it is possible to accurately assess clustering inside
a shaft furnace and obtain agglomerated ore having favorable characteristics based
on the assessment method of the present invention.
Brief Description of Drawing
[0014] FIG. 1 is a graph showing cluster strengths CS
0 (mass%) and CS
30 (mass%) of Examples 1 to 6 and Comparative Example 1.
Description of Embodiment
[0015] An embodiment of the present invention will be specifically described below. The
following embodiment illustrates a device and a method for embodying the technical
idea of the present invention, and is not intended to restrict the configuration to
the one described below. Thus, various changes can be made to the technical idea of
the present invention within the technical scope described in the claims.
<Agglomerated Ore Assessing Method of Embodiment>
[0016] Regarding an agglomerated ore assessing method of this embodiment, a specific assessment
method will be described below.
[0017] First, 500 g ± 5 g of an agglomerated ironmaking raw material (agglomerated ore)
is put through a sieve to measure a particle size distribution and determine the maximum
particle size of the agglomerated ore. Then, the agglomerated ore is placed in an
N
2 atmosphere and heated to a temperature of 1000°C at 5°C/min. (This temperature is
a predetermined temperature between 1000°C and 1200°C, which is 1000°C here.) Meanwhile,
a load is gradually applied such that a load of 1 kg/cm
2 is applied when 1000°C is reached. Then, while a load of 1 kg/cm
2 is still applied at 1000°C, the gas is switched to an N
2-20 vol% H
2 gas, and the agglomerated ore is held for three hours with this gas flowing at a
flow rate of 24 L/min. Then, the atmosphere is switched to an N
2 atmosphere and the agglomerated ore is cooled to room temperature. Thus, a reduced
aggregate is produced.
[0018] Next, the reduced aggregate is sifted using a sieve with an opening size corresponding
to the maximum particle diameter of the agglomerated ore before reduction, and the
reduced aggregate on the sieve and the reduced aggregate under the sieve are weighed.
Here, the mass of the reduced aggregate on the sieve is denoted by W(g). Then, the
reduced aggregate on the sieve is transferred to an I-type tumble tester (132 mmϕ
× 700 mm) and rotated 30 times at 30 rpm. Then, the reduced aggregate taken out is
put through the same sieve, and the reduced aggregate on the sieve and the reduced
aggregate under the sieve are weighed. Here, the mass of the reduced aggregate on
the sieve is denoted by W'
30(g). Thereafter, using the obtained W and W'
30, cluster strength CS
30 (mass%) is measured from Formula (3) below:

[0019] The rpm and the number of times of rotation of the I-type tumble tester may be adjusted
as necessary according to the impact applied to the sintered ore in the shaft furnace
used for reduction. When cluster strength in the case where treatment is performed
at the rpm and the number of times of rotation corresponding to the impact is denoted
by CS, cluster strength CS (mass%) can be measured from Formula (1) below using the
aforementioned W and the mass W' of the reduced aggregate on the sieve having undergone
the tumble treatment in the I-type tumble tester:

[0020] Thus, producing a reduced aggregate at 1000°C to 1200°C, both inclusive, allows an
accurate assessment of clustering in the case where hydrogen reduction is performed
while thermal compensation using blowing sensible heat is made.
[0021] As mentioned above, when the gas components include a compound having a C atom, such
as CO, CO
2, and methane, reduced iron becomes carburized and less prone to clustering. In the
case of reduction using a reducing gas of which the gas concentration of a compound
having a C atom is low and the H
2 concentration is increased, clustering cannot always be accurately assessed. In this
embodiment, on the other hand, clustering is assessed using a reducing gas that is
an N
2-20 vol% H
2 gas and does not contain a compound having a C atom. Thus, it is possible to accurately
assess clustering in the case where a reducing gas that does not contain a compound
having a C atom is used. Moreover, when such a reducing gas is used, as the number
of types of gases used is fewer than in the conventional method, the assessment can
be conducted in a simplified manner. From this viewpoint, in the agglomerated ore
assessing method of this embodiment, it is preferable that a reduced aggregate be
produced using a reducing gas that does not contain a compound having a C atom. Further,
it is preferable that a reduced aggregate be produced using a reducing gas containing
70 vol% or more H
2. Thus, reduction of agglomerated ore using a reducing gas with the H
2 concentration increased to 70 vol% or more can be simulated to assess clustering
in this reduction.
<Agglomerated Ore of Embodiment>
[0022] Agglomerated ore of this embodiment is characterized in that cluster strength CS
30 measured by the above-described agglomerated ore assessing method according to the
present invention is 0 mass%. When the cluster strength CS
30 is 0 mass%, the agglomerated ore is found to have favorable disintegratability at
high temperatures. Therefore, if this agglomerated ore is used to produce reduced
iron in a shaft furnace etc., clustering can be appropriately reduced even when a
reducing gas with an increased H
2 concentration is used.
[0023] In the agglomerated ore of this embodiment, it is preferable that the particle diameter
of the agglomerated ore be 8 mm or larger. When the particle diameter is 8 mm or larger,
the area of contact between the particles can be made smaller to further reduce clustering.
Here, a particle diameter of 8 mm or larger means a particle diameter of agglomerated
ore that remains on a sieve with a mesh size of 8 mm. It is preferable that total
Fe in the agglomerated ore be 64.5 mass% or less. Here, the total Fe refers to the
component concentration (mass%) of Fe contained in metal Fe and Fe compounds (iron
oxide, calcium ferrite, iron sulfide, etc.). Using an ironmaking raw material in which
the total Fe is 64.5 mass% or less can further reduce clustering. In addition, it
is preferable that the agglomerated ore meet Formula (2) below:

where Al
2O
3 is the component concentration (mass%) of Al
2O
3 in the agglomerated ore, and SiO
2 is the component concentration (mass%) of SiO
2 in the agglomerated ore.
[0024] Clustering occurs as metallic iron particles bind to one another in a solid phase.
When the component concentration of gangue components, such as Al
2O
3 and SiO
2, contained in the agglomerated ore increases, the iron concentration in the surfaces
of reduced iron particles decreases, so that solid-phase binding of metallic iron
particles is reduced and clustering is thereby reduced. Thus, agglomerated ore containing
a large amount of gangue components that meets Al
2O
3 + SiO
2 ≥ 3.5 mass% is reduced in clustering compared with conventional agglomerated ore
in which Al
2O
3 + SiO
2 < 3.5 mass% applies, and is therefore preferably used to produce hydrogen-reduced
iron.
Examples
[0025] Examples of the present invention will be described in detail below.
[0026] Agglomerated ores of Examples 1 to 6 and pellets of Comparative Example 1 were assessed
for clustering in accordance with the above-described agglomerated ore assessing method.
Table 1 below shows the sintering temperatures and the component compositions of the
agglomerated ores of Examples 1 to 6 and the pellets of Comparative Example 1. As
Comparative Example 1, pellets produced from a raw material that has been conventionally
used was used.
Table 1
|
Sintering temperature °C |
Total Fe mass% |
CaO/SiO2 mass% |
SiO2 +Al2O3 mass% |
Example 1 |
1150 |
63.94 |
0.38 |
5.84 |
Example 2 |
1250 |
64.12 |
0.37 |
5.87 |
Example 3 |
1350 |
64.00 |
0.37 |
5.82 |
Example 4 |
1150 |
63.40 |
0.75 |
5.72 |
Example 5 |
1250 |
63.45 |
0.76 |
5.72 |
Example 6 |
1350 |
63.47 |
0.77 |
5.68 |
Comparative Example 1 |
1350 |
65.22 |
0.27 |
2.72 |
[0027] For assessment of clustering, cluster strength CS
0 before the assessment and cluster strength CS
30 after 30 rotations were obtained. CS
0, which is before the tumble treatment, is 100.0 mass%. The assessment result is shown
in Table 2 below and Figure 1. The reduction temperatures and the reducing gas compositions
are shown in Table 2 below.
[Table 2]
|
Reduction temperature °C |
Reducing gas composition (vol%) |
CS0 (mass%) |
CS30 (mass%) |
Example 1 |
1000 |
N2-20%H2 |
100.0 |
0 |
Example 2 |
1000 |
N2-20%H2 |
100.0 |
0 |
Example 3 |
1000 |
N2-20%H2 |
100.0 |
0 |
Example 4 |
1000 |
N2-20%H2 |
100.0 |
0 |
Example 5 |
1000 |
N2-20%H2 |
100.0 |
0 |
Example 6 |
1000 |
N2-20%H2 |
100.0 |
0 |
Comparative Example 1 |
1000 |
N2-20%H2 |
100.0 |
57.0 |
[0028] As shown in FIG. 1 and Table 2, compared with Comparative Example 1 in which cluster
strength CS
30 is as high as 57.0 mass%, all the agglomerated ores of Examples 1 to 6 that meet
Al
2O
3 + SiO
2 ≥ 3.5 mass% have cluster strength CS
30 of 0 mass% and thus have proven to have favorable disintegratability. From this result,
the agglomerated ores of Examples 1 to 6 that meet Al
2O
3 + SiO
2 ≥ 3.5 mass% can be said to be agglomerated ores that are less prone to clustering,
and these agglomerated ores have been confirmed to be preferably used for hydrogen
reduction using a shaft furnace.
Industrial Applicability
[0029] The agglomerated ore assessing method of the present invention assesses clustering
at a higher temperature than the conventional method, and can thereby assess clustering
of agglomerated ore taking into account thermal compensation that is made using blowing
sensible heat in hydrogen reduction, which makes the present invention industrially
useful. Further, clustering inside a shaft furnace can be thus accurately assessed
and agglomerated ore having favorable characteristics can be obtained based on the
assessment method of the present invention, which also makes the present invention
industrially useful.