[0001] The present invention relates to a multi-step steelmaking refining method, comprising
refining steps, beginning when the molten pig iron is tapped from the blast furnaces
and ending when the molten steel is cast, carried out in a single reaction vessel,
wherein the decarburization of molten pig iron, which has been desiliconized and dephosphorized,
is carried out in the reaction vessel by means of oxygen which is soft-blown onto
the surface of the molten pig iron by a multi-aperture lance or a plurality of lances
while a stirring fluid is blown beneath the level of the molten pig iron within said
reaction vessel during the decarburization treatment.
[0002] The impurities of molten pig iron produced by a blast furnace are removed exclusively
in a converter, according to the conventional steelmaking refining method, by means
of pure-oxygen being blown into the converter. In other words, the function of removing
the impurities is concentrated on the converter refining. More specifically, the desiliconization,
dephosphorization, desulfurization and decarburization reactions proceed in a converter
concurrently or successively to one another. Since the impurities to be removed have
chemical properties different from each other, and since the removal reactions take
place concurrently or successively, it is not always possible for the conditions in
a converter to be suitable for the removal of each impurity to be removed. More specifically,
silicon, which is one of the impurities to be removed, is oxidized to Si0
2 usually in the initial oxygen-blowing period of a converter so that a slag layer
having a low basicity (the ratio of CaO/SiO
2) is formed. This slag having a low basicity is not suitable for the removal of phosphorus
and sulfur. In order to carry out the dephosphorization and desulfurization, the basicity
of the slag must be maintained at a high level. According to a practice employed for
this purpose, a large amount of auxiliary materials, mainly composed of lime, is incorporated
in a converter. This causes the generation of an enormous amount of slag, for example,
from 100 to 130 kg per ton of molten steel, which, in turn, brings about the following
problems.
1. Due to the large amount of slag generated in a converter, the slopping phenomena
during the blowing period is promoted and thus the recovery of iron is decreased.
When one attempts to prevent the slopping phenomena, it is necessary to install an
excessively large free-board, with the result that not only the weight of the converter
vessel and amounts of refractories used are increased, but also the time required
for the construction and repairing of converter vessel is increased. As a result,
low productivity occurs.
2. Iron oxide in the slag is increased proportionally to the amount of slag generated,
and, therefore, the recovery of iron is decreased.
3. In accordance with the increase in the amount of slag generated, heat lost as the
sensible heat of slag is increased and, thus, the thermal efficiency of the steel-making
refining process is decreased, which, in turn, leads to an unavoidable decrease in
the ratio of scraps to be loaded to the molten pig iron.
[0003] In order to eliminate the above-mentioned problems, it is possible to pretreat molten
pig iron before the converter refining so that various impurities are removed from
the pig iron. Two pretreatments have been mainly developed regarding the removal of
sulfur and phosphorus from the molten pig iron before it is put into the converter,
so that it is not necessary to carry out these processes in the converter. The desulfurization
and dephosphorization, which have been conventionally achieved in a converter, are
therefore replaced by the desulfurization and dephosphorization during the pretreatment
of the molten pig iron, according to recently developed steelmaking methods. In a
case when the desilidonization, which has been conventionally achieved in a converter,
is replaced with the desiliconization by pretreatment, it is possible to considerably
decrease the amount of a slag forming agent put into the converter and, thus, the
amount of the slag generated in the converter is also considerably decreased, thereby
further removing the problems mentioned above.
[0004] In the most advanced multi-step steelmaking refining method at present, the steps
of desiliconization, dephosphorization and decarburization are successively carried
out. Desulfurization can be carried out at any time of the steelmaking refining method.
For example, desulfurization can be carried out either once or twice simultaneously
with the dephosphorization step, between the desiliconization and dephosphorization
steps, or after the decarburization step. Even in this most advanced multi-step steelmaking
refining method however, decarburization is accomplished in a conventional converter
after the pretreatment of the molten pig iron for removing silicon, and phosphorus
and occasionally sulfur in a ladle or torpedo car has been completed. In this case,
since reloading of the melt is necessary at the time the molten pig iron is loaded
into a converter and tapped from the converter, such problems as generation of dust
at the reloading and lowering in the temperature due to reloading are caused, which,
in turn, causes a decrease in the thermal efficiency.
[0005] In addition, a problem occurs during decarburization in a conventional converter
according to the multi-step steelmaking refining method, since the amount of slag
generated in the converter is drastically smaller than the slag generated during the
conventional steelmaking refining method, so that when the molten pig iron, which
is virtually uncovered, is subjected to the decarburization blowing, it is likely
to eject upwards due to the oxygen jet. In the multistep steelmaking refining method,
such oxygen-blowing as that employed for the conventional converter would result in
a rather violent spitting and reduction in recovery of iron. To overcome the spitting
during the decarburization step in a multi-step steelmaking refining method comprising
a desiliconization step, desulfurization and dephosphorization and a step to decarburize
the molten iron whose silicon, sulfur and phosphorus contents have been reduced and
it is known from FR-A-2 439 821 to blow the gaseous oxygen softly onto the surface
of the bath, while simultaneously a gas is blowing into the reaction vessel from the
bottom in order to stir the bath of molten iron vigorously. The soft blowing can be
performed by a single or a multi-aperture lance.
[0006] It is an object of the present invention to provide a multi-step steelmaking refining
method, in which decarburization is carried out without causing the disadvantages
in the prior art and which leads to an increase in recovery of steel.
[0007] The object of the present invention is achieved by a multi-step steelmaking refining
method comprising refining steps, beginning when the molten pig iron is tapped from
the blast furnace and ending when the molten steel is cast, carried out in a single
reaction vessel, wherein the decarburization of molten pig iron, which has been desiliconized
and dephosphorized, is carried out in the reaction vessel by means of oxygen which
is softblown onto the surface of the molten pig iron by a multi-aperature lance or
a plurality of lances, while a stirring fluid is blown beneath the level of the molten
pig iron within said reaction vessel during step decarburization treatment, characterized
by the combination of blowing with said lance or lances and stirring with a power
of not less than 400 watts per ton in terms of the equation (s)=0.0285 (Q-T/W) log
(1+H/148), wherein:
Q is the flow rate of the stirring fluid in I/min,
T is the temperature of the melt in K,
W is the weight of the melt in tons, and
H is the depth of the stirring fluid blown in cm.
[0008] For the decarburization of the desiliconized and dephosphorized pig iron, no slag-forming
agent is necessary, as a rule, in a reaction vessel, such as a ladle, and therefore
it is possible to overcome the problems arising in the conventional converter steelmaking
method.
[0009] In other words, the molten pig iron, which is the starting material of the decarburization
treatment, is a pretreated molten pig iron which has been desiliconized and dephosphorized
and, occasionally, has also been desulfurized to a predetermined level. The molten
pig iron subjected to the pretreatment mentioned above has a silicon content of usually
not less than 0.20%, and desirably only a trace, and also has a phosphorus content
not exceeding the value specified regarding the finished steel. The present invention
is not limited to a specific pretreatment method, and any known pretreatment method
can be carried out. In addition, any known treatment of decarburization steel may
be carried out in the multi-step steelmaking refining method of the present invention.
This treatment, which is carried out after the decarburization treatment, is hereinafter
referred to as a post treatment. Regarding sulfur, the sulfur content can be decreased
to a value lower than the value specified for the finished steel by means-of the following
methods, which are selected depending upon the specific purpose of the steel. That
is, the molten pig iron can be subjected to a desulfurization pretreatment, a desulfurization
post treatment, or a combination of the desulfurization-pretreatment and post treatment,
which combination is employed for producing high grade steels required to have a low
sulfur content.
[0010] As described hereinabove, spitting is likely to occur when decarburization blowing
is carried out when no slag, or only a small amount of slag, is present on the surface
of the melt. The so-called soft blow, in which oxygen is calmly blown and transmitted
to the surface of the melt, effectively suppresses spitting. Incidentally, since,
in the method of the present invention, only decarburization is carried out while
on a melt slag is essentially absent, direct contact of the oxygen with the molten
pig iron is easy. Therefore, in an embodiment of the present invention, oxygen top
blowing is carried out by a super soft blow, which cannot achieve effective decarburization
in the conventional converter steelmaking method. It is also possible to drastically
suppress spitting, while the decarburization reaction is effectively promoted, due
to the stirring explained in detail hereinbelow.
[0011] According to the invention decarburizing is accomplished in a short period of time
in carrying out oxygen top blowing by means of a multi-aperture lance and/or a plurality
of lances, thereby dispersing the oxygen jet on the surface of the melt and thus decreasing
the depth of the cavity formed by the oxygen jet (L) of the oxygen jet into the melt.
Thus oxygen is supplied to the melt at a high rate and the advantages of the super
soft blow are maintained.
[0012] In the conventional converter steelmaking method, the oxygen jet is required to have
both a function of supplying oxygen to cause the refining reactions and a function
of stirring the melt so as to enhance the reaction efficiency. The oxygen jet of the
conventional converter steelmaking method, therefore, involves a problem in that the
stirring function, which should enhance and promote the reaction, leads instead to
spitting. In order to avoid such a problem, the two functions of the oxygen jet, mentioned
above, are distinctly divided so that the top blowing oxygen jet is provided only
to supply the oxygen and a stirring fluid is employed only to stir the melt. More
specifically, the super soft blow is so inadequate for stirring molten pig iron that
a large iron oxide layer tends to form on the surface of the melt, and, further, the
ratio of supplied oxygen combining with the carbon during decarburization, which is
referred to as the decarburization reaction ratio, is decreased. In order to maintaining
the advantages of the super soft blow and simultaneously eliminate the disadvantages
due to the absence of the stirring function, it is necessary to employ a stirring
method apart from the top blowing of the oxygen. This is achieved by introducing a
stirring fluid beneath the level of the molten pig iron in a reaction vessel.
[0013] In an embodiment of the present invention, the stirring fluid is blown through one
or more immersion lances.
[0014] In an embodiment of the present invention, the stirring fluid is blown through one
or more of tuyeres or gas-permeable plugs situated in the reaction vessel beneath
the level of the molten pig iron.
[0015] The blowing rate of the stirring fluid must be such that a stirring state, in terms
of stirring power, of at least 400 watt/ton, preferably at least 800 watt/ton, be
ensured. The stirring power is calculated by the following equation

wherein:
Q is the flow rate of the stirring fluid in I/min;
T is temperature of the melt in K;
W is the weight of the melt in tons; and,
H is the depth the stirring fluid is blown in cm.
[0016] It is not necessary to maintain a stirring power of at least 400 watt/ton over the
entire decarburization blowing period, but it is necessary to do so at least during
the initial or early stage.
[0017] The decarburization blowing, in which spitting is drastically suppressed due to the
super soft blow, is advantageously achieved in the present invention, and, therefore,
a considerably greater amount of molten pig iron can be loaded in a converter than
that able to be loaded in a conventional converter refining method.
[0018] In an embodiment of the present invention, the reaction vessel mentioned above is
a ladle for molten pig iron, which may be provided with a means for blowing the stirring
fluid, and this ladle contains the molten pig iron in a filling ratio which is of
a usual value. The usual amount of molten pig iron loaded in a pig iron ladle, for
example from 60 to 80% based on the volume of the pig iron ladle, is considerably
higher than the usual amount of molten pig iron loaded in a converter according to
a conventional decarburization blowing method. Although the decarburization blowing
method according to said embodiment is carried out under a high loading condition,
the decarburization blowing can be carried out effectively without causing a decrease
in the recovery of iron. It is therefore unnecessary according to the decarburization
blowing method of the present invention, to use such an excessively large apparatus
as a converter, since the steelmaking refining steps can be effectively carried out
in a compact apparatus or apparatuses.
[0019] By using the single reaction vessel mentioned above, the steps starting at receiving
the molten pig iron from a blast furnace and ending at the casting of the molten steel
can be carried out. These steps may include successively the desiliconization step,
the dephosphorization or simultaneous dephosphorization and desulfurization step,
and the decarburization step. In the embodiment now described the reaction vessel,
such as a molten pig iron ladle, has both a role of transporting the melt and a role
of supplying a place where the refining reactions take place. It is therefore possible
to continuously use the reaction vessel from a time when the reaction vessel receives
the molten pig iron from the blast furnace until a time when either the continuous
casting method or the usual casting method for forming ingots is carried out, without
reloading the melt. Between the two times mentioned above, the treatments of desiliconization,
dephosphorization, desulfurization and decarburization can be carried out by a multi-step
refining method. In a steelmaking plant, in which torpedo cars are installed, the
desiliconization step and the dephosphorization, or simultaneous dephosphorization
and desulfurization step, can be successively carried out in the torpedo cars, and
subsequently, before the initiation of the decarburization step, the molten pig iron
is reloaded from the torpedo cars into a reaction vessel, which is a reaction vessel
other than the torpedo cars. The decarburization blowing is then carried out in the
reaction vessel. If necessary, the desulfurization and adjusting of the steel chemistry
can be carried out in this reaction vessel, followed by a casting step. In the multi-step
steelmaking refining method by means of torpedo cars and a reaction vessel, the melt
must be reloaded once. However, this method is also advantageous, because the decarburization
step is carried out according to the present invention.
[0020] Methods for decreasing the times of reloading the melt or making the reloading unnecessary
are previously known. According to one of these methods, known in Japanese laid-open
patent application No. 54-130420, a ladle receives the molten pig iron tapped and
this molten pig iron is directly loaded in a converter without reloading of the melt.
According to another known method, molten pig iron, which has been desiliconized,
dephosphorized and desulfurized in one vessel, is decarburized in a converter. According
to another method, known from Japanese laid-open patent application No. 51-27811,
refining is continuously carried out in a transportable refining ladle. However, since
in the former two methods a converter is necessary in a sequence of the refining steps,
two reloading operations are necessary, i.e. at the step of reloading into the converter
and at the step of reloading from the converter into a casting ladle. These two methods,
therefore, still involve problems in that a large amount of heat is lost and dust
is generated during the reloading operations. In addition, since the decarburization
blowing of these two methods is a conventional method of decarburization, the recovery
of iron is low. In the latter method, although the problems of heat loss and dust
generation are solved, various problems resulting from slag, such as a large amount
of the slag generated, remain unsolved because the molten pig iron is not pretreated
and is subjected to the steelmaking reactions which are basically the same as the
conventional ones.
[0021] In an embodiment of the present invention, the stirring fluid is at least one member
selected from the group consisting of carbon dioxide gas, argon, nitrogen gas and
oxygen gas. The nitrogen gas, however, should not be used for producing a grade of
steel in which the nitrogen content is required to be very low. Since the oxygen may
erode the refractories of the gas-permeable plugs, the cooling of such plugs is advisable.
[0022] In an embodiment of the present invention, a removable free board is installed on
the reaction vessel at the decarburization period.
[0023] Several of the embodiments will now be described more quantitatively or specifically.
[0024] In the super soft blowing, a characteristic parameter of the oxygen jet (UL
o) cannot be more than 0.3, wherein L
o is the depth of a stationary melt within a reaction vessel in mm and L is the depth
of the cavity formed by the oxygen jet in mm determined by the following formulae.

and

[0025] In these formulae:
L is an infiltration depth of the oxygen jet into the melt in mm;
h is the distance between the lance(s) and the surface of the melt in mm;
Fo2 is the flow rate of oxygen in Nm3/h;
n is the number of apertures (nozzles) in each lance;
d is the diameter of each aperture (nozzles) in mm; and
k is the calibration coefficient depending upon the injection angle 0 from the lance
axis as follows.
[0026] In a case when n is 1 (n=1 ), k=1.0. In a case when n is 2 or more (n?2), k=
1.7 at θ=
0°, k=
1.
4 at θ= 6°, and k=1.0 at θ=10°.
[0027] In the conventional converter, the depth of a stationary melt within a converter
(L
o) is, at the highest, from approximately 0.1 to 0.3 times the effective inner height
of the converter (L
t), and, therefore, most of the effective inner height (L
t) of the converter is a so-called free board, where the converter wall does not come
in contact with the melt. According to the present invention, in which heavy loading
in the decarburization step is achieved, the ratio of L
°/L
t can be 0.6 or more (L
°/L
t≧0.6). In this case, the maximum ratio of L
°/L
t is limited, so that height of the melt, which is stirred due to the decarburization
blowing, does not exceed the height of the free board. When the maximum height of
the stirred melt measured from the level of the stationary one during the decarburization
blowing is expressed by L
S, the maximum ratio of L
°/L
t is limited, so that the relationship of L
°/L
t,<1-L
s/L
t is satisfied. If the heavy loading of present invention is carried out in the conventional
converter steelmaking method, problems caused by swelling of the slag, slopping and
spitting become serious. Therefore, in the conventional converter, the loading of
pig iron is limited, so that the relationship of L
°/D
°<0.5 is satisfied, wherein Do is the effective inner diameter of the converter. Contrary
to this, the decarburization blowing is possible, even in a case when L
°/D
°≧0.5. This means that the decarburization treatment capacity of a reaction vessel
having a predetermined dimension can be significantly increased, as compared with
that in the conventional converter refining method, which is a commercially useful
point.
[0028] In order to stir the melt, not only gas, but also liquid, such as liquid oxygen and
liquid carbon dioxide, as well as mixture of a gas and a liquid can be used as the
stirring fluid. The volume expansion at the gasification of the liquid is highly effective
for stirring the melt.
[0029] As understood from the description hereinabove, the multi-step steelmaking refining
method of the present invention comprises a novel decarburization step-which does
not rely at all on the conventional converter steelmaking method. Since one of the
advantages of the present invention resides in a very simplified process starting
at the receipt of the molten pig iron from a blast furnace and ending at the pouring
and solidification of the steel, the present invention is greatly advantageous to
the steelmaking industry.
[0030] The preferred embodiments of the present invention will now be described with reference
to the following drawings.
Fig. 1 and Fig. 2 schematically illustrate preferred embodiments of the multi-step
steel making refining method of the present invention.
Figs. 3 through 5 illustrate reaction vessels in which the decarburization blowing
is being carried out.
Fig. 6 is a graph illustrating the relationship between the characteristic parameter
of the oxygen jet of (ULo) and the decarburization ratio which defines the carbon
decarburization reaction ratio, relative to the amount of oxygen supplied. In Fig.
6, the relationship is shown between the characteristic parameter of oxygen jet (ULo) and the amount of molten steel scattered out of a reaction vessel due to spitting,
etc. In Fig. 6, the ratios of L°/Lt according to the present invention and the conventional method are 0.7 and 0.2, respectively.
[0031] Referring to Figs. 1 and 2, it will be understood that the multi-step refining is
carried out in the following sequence:
I-A reaction vessel receives molten pig iron from the blast furnace (BF).
II (Desiliconization Step) The desiliconization is carried out, for example by means
of the oxygen injection method.
III (Dephosphorization and/or Desulfurization Step) For example, a method of admixing
flux by means of a mechanical stirring method or an oxygen-injection method while
incorporating flux is carried out.
IV (Decarburization Step) Decarburization by the super soft blow method is carried
out and the melt is stirred by a stirring fluid, which is, for example, blown through
an immersion lance.
V (Adjusting Step of Steel Chemistry) For example, RH degassing is carried out.
VI (Casting Step) Finished steel is cast by a continuous casting method.
VII The reaction vessel is hot-repaired and waits the tapping from the blast furnace.
[0032] It will be apparent from the above description that one reaction vessel has the roles
of transporting, storing, pouring and being the place where the refining reactions
take place. In Fig. 1, the stations of refining, casting and the like are arranged
linearly, while in Fig. 2 these stations are arranged in a circle.
[0033] Referring to Fig. 3, a preferred embodiment of the decarburization blowing is schematically
illustrated. In Fig. 1, the reaction vessel is composed of the metal shell 1a and
refractory lining 1 b and contains therein the melt 2.
[0034] The depth of the melt 2 is L
o when the melt is stationary. The reaction vessel has the effective inner height L
t which is shown in Fig. 3. The oxygen is blown through the top blowing lance 3 by
a super soft blow. One gas-permeable refractory plug 4 is provided at the bottom of
the reaction vessel 1 so as to blow the stirring fluid into the melt 2. The oxygen
blown from the top blowing lance 3 makes the cavities onto the melt 2 by a depth of
L. The melt 2 is basically molten pig iron, since if the slag forming agent is used,
it is used only to the extent that the oxides resultant from the oxygen blowing cannot
erode the refractory lining 1 b. The symbols of HF and Do in Fig. 3 denote the height
of the freeboard and the effective inner diameter of the reaction vessel. If necessary,
a plurality of the top blowing lances 3 and a plurality of the gas-permeable refractory
plugs may be used.
[0035] Referring to Fig. 4, three top blowing lances 3 are used for blowing the oxygen and
the bottom of reaction vessel 1 is provided with two blowing tuyeres 5 instead of
the gas-permeable refractory plug 4 for blowing the stirring fluid. Referring to Fig.
5, two top blowing lances 3 are used for oxygen blowing and the stirring fluid is
blown through the immersion lance 6. A removable side wall, i.e. free board 7, is
installed on the reaction vessel, so as to form an inner space 8 defined by the inner
wall of the free board 7 and thus spitting of melt 2 out of the inner space 8 is prevented.
[0036] Referring to Fig. 6, the present invention and conventional methods having different
ratios of LJL, different from one another are compared with one another regarding
the amount of melt scattered out of the reaction vessel and the variation of the decarburization
reaction ratio vary depending upon the characteristic parameter of oxygen jet (UL
o). In Fig. 6, the ratios of LolL! of the present invention and conventional methods
are 0.7 and 0.2, respectively. In case of the conventional converter, the characteristic
parameter of oxygen jet (UL
o) is usually set between 0.7 and 1.0. As is apparent from Fig. 6 the super soft blow
of present invention in terms of characteristic parameter of oxygen jet (UL
o) is not more than 0.3, which isthe preferable maximum value for keeping the recovery
of iron, and the decarburization reaction in the conventional converter steelmaking
method virtually does not take place. More specifically, the term "super soft blow"
can be explained by the concept that the decarburization reaction ratio is virtually
zero when the melt is not subjected to stirring by the stirring fluid blown into the
melt.
[0037] As is also apparent from the lower half of Fig. 6, the decarburization reaction ratio
is at the ideal level. This is because the oxygen is brought into a direct contact
with the melt and the stirring mentioned above is carried out.
[0038] The present invention will now be explained by way of Examples.
Example 1
[0039] Table 1 shows the average steel chemistry of six heats, when the multi-step steelmaking
method comprising the desiliconization, simultaneous dephosphorization and desulfurization,
and decarburization steps were carried out. Each heat consisted of 60 ton of molten
pig iron and 6 ton of scraps. An increase in the phosphorus content after the decarburization
step is not considered to be the result of rephosphorization. The recovery of iron
and the amount of slag generated are shown in Table 2.

[0040] The term "Conventional (A)" in Table 2 indicates a conventional converter steelmaking
method.
Example 2
[0041] The procedure of Example 1 was repeated except for the decarburization step as is
apparent from Table 3. The recovery of iron by the present invention is considerably
higher than that of the comparative tests.

Example 3
[0042] In the present example, the multi-step refining method comprised the desiliconization,
dephosphorization, decarburization and desulfurization steps. The resultant steel
chemistry and refining condition in each step are shown in Table 4, and the recovery
of iron and amount of slag generated are shown in Table 5.

Example 4
[0043] The procedure of Example 3 was repeated except for the decarburization step as apparent
from Table 6.

Example 5
[0044] In the present example shown in Table 7 "Invention" indicates the decarburization
blowing of the desiliconized, dephosphorized and desulfurized molten pig iron which
was loaded in a reaction vessel at the ratio of L
°/L
t=0.7. In addition "Conventional" indicates a conventional converter refining of molten
pig iron which was loaded in the converter at the ratio of L
°/L
t=0.2. In the method of the present invention, the - amount of slag generated is very
small because no auxiliary raw materials are used at all, and the recovery of iron
is high.

Example 6
[0045] In the present example shown in Table 8, "Invention" and "Conventional" indicate
the decarburization blowing method, in which the liquid oxygen was blown as the stirring
gas, and the decarburization blowing method, in which no stirring gas was blown, respectively.

[0046] As will be understood from the description hereinabove, especially the Examples,
an excessively large apparatus, such as a converter, is no longer necessary in refining
pig iron and an increase in the recovery of iron can be achieved, according to the
present invention. Since reloading of the melt is no longer necessary or if necessary,
reloading is limited to only one or possibly two times, the generation of dust is
decreased and thermal efficiency is increased. Since the amount of slag generated
in accordance with the method of the present invention is considerably smaller that
generated in the conventional converter steelmaking method, the slag processing apparatus
can be very compact.
[0047] Furthermore, the free oxygen content of the steel at the end of the oxygen blowing
process is lower as compared with that the conventional steelmaking method, which
contributes to the recovery of alloying elements, as well as to the recovery of iron.