U.S. patent number 3,854,932 [Application Number 05/370,904] was granted by the patent office on 1974-12-17 for process for production of stainless steel.
This patent grant is currently assigned to Allegheny Ludlum Industries, Inc.. Invention is credited to Harry L. Bishop, Jr..
United States Patent |
3,854,932 |
Bishop, Jr. |
December 17, 1974 |
PROCESS FOR PRODUCTION OF STAINLESS STEEL
Abstract
A process is disclosed for the production of stainless steel
wherein a chromium-containing melt suitable for producing stainless
steel is blown with oxygen in an oxygen converter, and an inert gas
is introduced through at least one tuyere in the bottom of the
converter while the interior of the converter above the liquid
level is maintained at subatmospheric pressure.
Inventors: |
Bishop, Jr.; Harry L.
(Pittsburgh, PA) |
Assignee: |
Allegheny Ludlum Industries,
Inc. (Pittsburgh, PA)
|
Family
ID: |
23461664 |
Appl.
No.: |
05/370,904 |
Filed: |
June 18, 1973 |
Current U.S.
Class: |
75/512;
75/555 |
Current CPC
Class: |
C21C
7/0081 (20130101); C21C 5/005 (20130101); C21C
5/35 (20130101); Y02P 10/143 (20151101) |
Current International
Class: |
C21C
5/30 (20060101); C21C 5/35 (20060101); C21C
7/00 (20060101); C21C 5/00 (20060101); C21c
005/34 (); C21c 007/10 () |
Field of
Search: |
;75/49,59,60 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Rutledge; L. Dewayne
Assistant Examiner: Rosenberg; Peter D.
Attorney, Agent or Firm: Giola; Vincent G. Dropkin; Robert
F.
Claims
What is claimed is:
1. A process for producing stainless steel comprising:
A. providing a charge that is a least partly liquid and suitable
for producing a chromium-containing stainless steel in an oxygen
steel converter having a tuyere in its bottom section,
B. introducing oxygen through a lance onto or beneath the surface
of said charge,
C. introducing an inert gas or an endothermic gas through said
tuyere,
D. maintaining a subatmospheric pressure in said converter, and
E. recovering a stainless steel product.
2. The process of claim 1 wherein the inert gas comprises argon
introduced at a rate of about 5-100 scfm.
3. The process of claim 1 wherein the inert gas is introduced at a
pressure of at least 100 psi.
4. The process of claim 1 wherein the tuyere is substantially on
the diameter of the converter bottom that lies in the same plane as
the horizontal axis of rotation of the converter.
5. The process of claim 1 wherein the pressure maintained in said
converter is at most 100 mm Hg absolute.
6. The process of claim 1 wherein the stainless steel product
contains less than 0.02 percent w carbon, and the final pressure in
said converter is at most 20 mm Hg absolute.
7. The process of claim 1 wherein, subsequent to the introduction
of oxygen but prior to recovering a product, the contents of said
converter are contacted with a reducing slag.
8. The process of claim 1 wherein oxygen is introduced through said
lance at progressively diminishing rates.
9. The process of claim 1 wherein the pressure in said converter is
progressively diminished.
10. The process of claim 1 wherein said inert gas is argon, and it
is introduced through said tuyere after oxygen introduction is
terminated and while a subatmospheric pressure is maintained in
said converter, whereby the nitrogen content of the stainless steel
is diminished.
11. The process of claim 1 wherein said endothermic gas is water
vapor.
12. The process of claim 1 wherein said endothermic gas is carbon
dioxide.
13. The process of claim 1 wherein said inert gas or endothermic
gas is introduced through a plurality of tuyeres in the bottom
section.
Description
BACKGROUND OF THE INVENTION
The well-known oxygen steel process is effected by blowing
substantially pure oxygen through a lance onto or slightly below
the surface of molten iron maintained in a basic oxygen converter.
The process is an improvement over Bessemer converters because it
produces a far superior product, and it is an improvement over open
hearth converters because of high production rates per unit of
capital and per unit of time that are obtainable by the basic
oxygen process. The process may be employed for making plain carbon
steel and for making stainless steel.
In the oxygen steel process, relatively pure oxygen is blown onto
the liquid bath that is maintained at high temperature. Although a
stream of pure oxygen simply impinges on the surface of the bath,
the exhaust gases from the process contain substantially no oxygen.
The high temperature molten metal bath is extremely active
chemically, and there are many reactions competing for the oxygen.
Among these, for producing stainless steel, are the reaction of
iron with oxygen to produce iron oxide, the reaction of chromium
with oxygen to produce chromium oxide, the reaction of carbon with
oxygen to produce carbon oxides and the reaction of various other
ingredients such as aluminum, silicon and manganese to produce
their respective oxides which generally become part of a slag
phase.
Of the various reactions mentioned above, the primary reason for
the refining process is to effect the reaction between carbon and
oxygen for the purpose of removing carbon from the liquid metal.
The reaction between oxygen and iron is desirably avoided because
it represents a loss of iron product. The reaction between oxygen
and chromium also should be avoided because it results in a loss of
chromium from the molten metal phase to the slag phase, and the
presence of chromium oxides in the slag phase creates a viscous
slag which interferes with the metal refining process. A viscous
slag is undesirable because it shields the surface of the molten
metal bath which retards the escape of carbon oxides and therefore
interferes with the removal of carbon from the melt as will be
described more fully hereinafter.
In the oxygen steel process apparently the oxygen introduced
through the lance impinges on the liquid phase within the converter
and reacts with carbon, chromium, iron and anything else capable of
being oxidized. It is thought that the oxygen doesn't necessarily
react directly with carbon but rather becomes part of an oxygen
inventory within the converter. At the conditions prevailing during
conversion there is vigorous stirring and oxygen is mobile. For
example, oxygen impinging against the surface may react with iron
to form an iron oxide which becomes part of the oxygen inventory
within the converter, but the iron oxide may react with carbon to
produce iron and carbon oxide so that the ultimate effect of the
oxygen is to produce a carbon oxide. The thermodynamics of the
system will determine, among other things, what compounds are
formed. For example, carbon and oxygen may react to form either
carbon dioxide, carbon monoxide or both. The thermodynamics at the
condiditons within the converter are such that the equilibrium
distribution between carbon monoxide and carbon dioxide is such
that more than 90 percent of the carbon oxide formed will be carbon
monoxide.
An entirely different effect is caused by the mass action
principle. According to the mass action principle, the distribution
between reactants and products is affected rather than the
distribution between various products. For example, oxygen may
react with carbon to form carbon oxide in the system. Thus, to
promote a reversible reaction it is necessary, according to the
mass action principle, to remove the reaction products and
therefore drive the reaction toward making more of them. In the
various reactions noted above which compete for the available
oxygen, both the affinity of oxygen for the different ingredients
in the melt and the concentration of the reaction products of the
various reactions are involved in determining which of the
ingredients of the converter will react with oxygen.
To promote the reaction of oxygen with carbon, many variations of
the oxygen steel process have been attempted. Among these are
introducing oxygen below the surface of the melt so that the
bubbles of oxygen may be distributed throughout the melt and
therefore oxygen is available to carbon throughout the melt, and
the introduction of mixtures of oxygen and inert gas, e.g. argon,
so that the bubbles of oxygen will not become too concentrated with
carbon oxides as the reactions proceed. However, the intense heat
of the oxidation generally causes oxygen or argon-oxygen mixtures,
which are introduced beneath the surface of the melt, to burn or
otherwise destroy the tuyeres or porous plugs through which the gas
mixtures are introduced; and in order to reduce the concentration
of carbon oxides significantly within the bubbles, extremely large
volumes of argon are required, in the range of 500 scf/ton of steel
refined. Also, oxides may form in the vicinity of the tuyeres which
can flux the lining as they rise to the surface of the bath thereby
decreasing lining life.
THE INVENTION
The process of this invention provides an economical and effective
means to solve or greatly mitigate the abovenoted problems. The
process of the present invention is a process for producing
stainless steel by the oxygen steel process which includes
providing a liquid charge suitable for producing
chromium-containing stainless steels in an oxygen steel converter
having a tuyere in its bottom, introducing oxygen into the
converter through a lance so that it impinges against or is
introduced beneath the surface of the liquid charge in the
converter, introducing an inert or endothermic gas through the
tuyere in the bottom of the converter, and maintaining a
subatmospheric pressure within the converter. Although a liquid
charge is referred to, the charge may be a mixture of liquid and
solid material.
The term inert gas is intended to define a gas that does not
participate to any significant extent in the reactions taking place
in the converter. Typical insert gases are argon and nitrogen. The
term endothermic gas is intended to define a gas that experiences
an endothermic reaction in the bath but neither the gas nor its
reaction products affect the metal product. Water (steam), which
breaks down to hydrogen and oxygen at the conditions within the
bath, and CO.sub.2, which becomes oxygen and carbon monoxide, are
two typical endothermic gases. Argon is the preferred gas where
low-nitrogen steels are to be made. In a preferred embodiment, one
or more tuyeres in the bottom of the converter are located on or
near the center line of the bottom that lies in the same plane as
the axis of rotation of the converter so that the tuyere is above
the liquid level in the converter when the converter is tilted one
way or another for loading or discharging. It is also preferred to
introduce argon or other inert gas at a relatively high pressure so
that expansion of the gas at the tuyere will produce a local
cooling effect which will prevent or at least diminish damage to
the tuyere from the heat of the surrounding molten charge.
Also, reference to tuyere(s) in the "bottom section" of the
converter as used in the specification and claims is intended to
include the side walls of the converter at or near the actual lower
most surface. Thus, the tuyeres may either by inserted through the
lining horizontally or vertically. In the horizontal case, the
lining life will probably be poorer than when the tuyeres are
centrally located, but mixing may be more thorough.
The converter must be maintained at subatmospheric pressure during
the conversion process of this invention. Subatmospheric pressure
is maintained by employing a sealed hood and providing a forced
exhaust system capable of removing gaseous reaction products and
inert gas at a sufficient rate to maintain the desired
subatmospheric pressure. Preferably, the pressure in the conversion
vessel will be progressively decreased as the conversion proceeds.
Pressures of at most 100 mm Hg must be maintained, but lower
pressures will frequently be required depending on the final alloy
chemistry desired. For example, when carbon contents of 0.02
percent or lower are desired, a vessel pressure lower than 20 mm Hg
will usually be required.
As stated above, it is desirable to effect the reactions in an
oxygen steel converter so that the oxygen reacts with carbon to the
exclusion of reactions between oxygen and iron and oxygen and
chromium. It is an objective of the present invention to promote
the oxygen-carbon reaction, and the process of the present
invention provides at least four means to promote that reaction and
to diminish the others. First, effecting the conversion under
subatmospheric pressure favors removal of vapor phase materials
from the converter. Since the reaction of oxygen and carbon
produces mostly carbon monoxide and a small amount of carbon
dioxide and since both of these products are gases, the operation
of the converter under subatmospheric pressure causes oxygen to
react with carbon to a greater extend than if the process were
effected at atmospheric or superatmospheric pressures.
Second, even under vacuum the liquid-static head of the melt is
considerable and the mass transfer of carbon oxides through the
melt is time consuming. The introduction of an argon stream below
the liquid creates bubbles of gas within the melt in which there is
a very small partial pressure of carbon oxide. In effect, each
bubble of argon is an in situ carbon oxide vacuum which causes the
carbon oxide to leave the melt and enter the bubbles, thereby
driving the oxygen inventory toward carbon oxide production even at
the higher pressures below the surface of the melt.
Third, the bubbles of gas rising through the melt create violent
agitation thereby exposing all portions of the molten material in
the converter to the subatmospheric pressure at the surface thereby
promoting the release of carbon oxides and the escape of them from
the converter again, thereby driving the oxygen inventory toward
the production of carbon oxides.
Fourth, by driving the oxygen inventory toward the reactions with
carbon rather than other materials, the formation of chromium oxide
is minimized, and as a result the slag phase is less viscous,
facilitating exposure of the molten metal to the subatmospheric
pressure to promote the escape of carbon oxides from the surface of
the melt. It is also an objective of this invention to minimize
erosion of refractory linings by promoting reactions within the
bath at locations remote from the refractory linings.
DETAILED DESCRIPTION OF THE INVENTION
An embodiment of the invention will be described with reference to
the accompanying drawings.
FIG. 1 is a sectional elevation view of a device suitable for
carrying out the process of the present invention taken along the
line 1-1 of FIG. 2.
FIG. 2 is a sectional plan view of the device illustrated in FIG. 1
taken along the line 2-2.
FIG. 3 is a sectional elevation view of the device illustrated in
FIG. 1 in position where molten metal is being discharged from the
converter.
The drawings illustrate a converter 10 which is formed of a steel
shell 11 and a refractory lining 12. The converter is equipped with
a supporting ring 13 upon which axles 15 are mounted for rotating
the converter around a horizontal axis so that it may be tilted for
loading and unloading. The converter is equipped with a lance 16
which extends through a hood 17 via a flanged fitting 18. The hood
seals against the top of the converter by bearing against a sealing
ring 20 through a gasket 21.
Through the bottom of the converter 10 two tuyeres 22 are
illustrated which are connected via lines 23 to a header 25 which
supplies lines 23, and accordingly tuyeres 22, with argon. A charge
26 that is at least partly liquid is maintained in the converter
through which argon bubbles 27 pass.
The process of the present invention is initiated with the hood 17
and lance 16 withdrawn to a position well above the converter 10.
The converter 10 is rotated on the axles 15 to a tilted position
wherein it receives a charge suitable for the production of
stainless steel. The charge includes molten iron, contains 0-30
percent chromium, 0-80 percent nickel, 0.1-7 percent carbon and the
usual impurities and conventional slag forming materials. During
charging, the tuyeres 22 are above the liquid level for the most
part; however, to insure maintaining the tuyeres open, a constant
flow of gas, preferably air or nitrogen because they are
inexpensive, is maintained through the tuyeres to avoid any
possibility of molten metal entering them.
When all of the charge is in the converter, it is rotated around
axles 15 and returned to its uprignt position as illustrated in
FIG. 1. The hood 17 is lowered to seal against the sealing ring 20
and the lance 16 is inserted through the flanged fitting 18 and
lowered to a position immediately above the surface of the liquid
charge as illustrated in FIG. 1. An exhaust device which is not
shown is placed into operation to draw gases out of the hood 17 and
the converter 10 to the extent that a subatmospheric pressure as
previously described is maintained in the converter.
Conversion is effected by blowing oxygen through the lance onto the
surface of the molten charge with sufficient force to cause a
dimple in the surface of the charge as illustrated at 28. A
separate slag phase is not shown although one will exist in
operation. During the oxygen blowing portion of the conversion,
argon gas is passed through header 25, and ultimately through
tuyeres 22, and bubbles violently through the molten metal
maintained in converter 10. Preferably, the argon is introduced at
a high pressure, at least 100 psi, so that it expands as it enters
the molten metal bath to create a cooling effect immediately in the
vicinity of the tuyeres thereby preserving the refractories in that
area. Argon is introduced at a rate of from 5-100 scfm. As
explained hereinabove, the low partial pressure of carbon oxides in
the bubbles 27, the violent agitation effected by the rising
bubbles of argon which exposes all portions of the molten metal 26
to the surface of the converter 10 all tend to drive the reaction
of oxygen with carbon rather than with iron or chromium and as a
result there is very little formation of detrimental chromium
oxides or wasteful iron oxides and a high production of carbon
oxides per unit of oxygen introduced.
Upon completion of the conversion, it may be desirable to mix some
natural gas with the argon passing through tuyeres 22 to deoxidize
the melt, after which the lance 16 is withdrawn, the hood 17 is
raised, and the converter tilted to a position shown in FIG. 3 to
discharge molten metal through the pouring spout 30. During
conversion, the pouring spout 30 is provided with a vacuum cap to
prevent air from being drawn into the converter and to prevent the
liquid charge from splashing out.
The product from the process may be a ferritic or austenitic
stainless steel or nickel superalloy.
As a specific example of this invention, a process embodying the
invention was employed to produce stainless steel containing a
maximum of 0.025 percent carbon, from 1.5-1.9 percent manganese,
from 0.3-0.6 percent silicon, from 18-19 percent chromium, from
8.75-10 percent nickel, a maximum of 0.04 percent phosphorus and
0.015 percent sulfur.
The process was initiated by tilting the vessel and charging it
with 153,000 pounds of molten metal containing 0.96 percent carbon,
0.94 percent manganese, 0.031 percent phosphorus, 0.015 percent
sulfur, 0.38 percent silicon, 19.05 percent chromium, 9.25 percent
nickel and the balance substantially iron. Although the entire
charge in this case was molten metal, the process may be effected
using a charge that is partly molten and partly solid. The solid
portion of the charge may include stainless steel scrap,
ferrochromium alloys or other solid metal-bearing materials.
While charging the vessel, argon gas was passed through the bottom
tuyeres to prevent fouling of those tuyeres by molten metal. Argon
gas was introduced at a rate of 15 scfm. Nitrogen, carbon dioxide
or even air may be passed through the tuyeres at this point in the
process to conserve expensive argon. At this point in the process,
when the hood is not sealed to the vessel and the vessel is in a
tilted position, it is convenient to measure the temperature of the
bath. In the process described herein, the temperature of the bath
after charging was 2,820.degree. F.
When the charging of the vessel was complete, the vessel was
rotated to vertical position and the hood was engaged with the top
of the vessel to create a seal capable of holding a vacuum. The
lance was lowered to a height of 40 inches above the surface of the
bath, the vacuum system was started and oxygen was blown through
the lance at a rate of 1,000 scfm. The vacuum system was operated
to maintain an absolute pressure within the vessel of 180 mm Hg. A
permissable variation of the process of this invention is to start
the oxygen blow before a vacuum is provided in the vessel so that
the initial carbon burn is effected at atmospheric pressure. It is
also a permissable variation of the process to deslag the vessel
after a short atmospheric oxygen blow after which a subatmospheric
oxygen blow is effected.
The oxygen blow was effected at progressively decreasing oxygen
rates and progressively lower absolute pressures. Oxygen was blown
into the vessel at 1,000 scfm under a chamber pressure of 180 mm Hg
for a period of 10 minutes after which the oxygen blow rate was
reduced to 850 scfm and the chamber pressure was diminished to 150
mm Hg. After 17 minutes at that rate, the oxygen blow rate was
diminished to 700 scfm and the chamber pressure diminished to 135
mm Hg, and 5 minutes later the chamber pressure was diminished to
50 mm Hg. After another 5 minutes, the oxygen blow rate was
diminished to 450 scfm and the chamber pressure diminished to 35 mm
Hg, and after another 9 minutes oxygen blowing was terminated, and
the chamber pressure was diminished to 6 mm Hg.
In order to reduce the nitrogen content of the steel, the argon
flow rate was then increased to 30 scfm and the chamber pressure
progressively reduced to 0.6 mm Hg over a period of 16 minutes,
after which the vacuum seal was broken and the vessel was rotated
in order to take a test sample and to measure the bath temperature.
The test sample was analyzed to determine what later additions
would be required to adjust the chemistry, and the bath temperature
was found to be 3,080.degree. F. The sample was found to contain
0.009 percent carbon, 0.58 percent manganese, 0.03 percent
phosphorus, 0.014 percent sulfur, 18.4 percent chromium, 9.38
percent nickel and 0.08 percent silicon.
While the vessel was in its rotated position, 1,500 lbs of 50
percent ferrosilicon, 3,000 lbs of burnt lime and 450 lbs of
fluorspar were added as a slag reduction mix. The vessel was
returned to vertical position, and the contents were stirred with
argon bubbles. The ferrosilicon in the reduction mix reduced the
chromium oxide in the slag and returned the chromium to the metal
phase while the burnt lime and fluorspar maintained the slag fluid.
After the slag has been thoroughly reduced, the vessel was tipped
again and deslagged, the bath temperature was measured and another
metal sample was taken. This metal sample was analyzed and found to
contain 0.009 percent carbon, 0.75 percent manganese, 0.03 percent
phosphorus, 0.012 percent sulfur, 18.7 percent chromium, 9.35
percent nickel and 0.54 percent silicon, and the temperature of the
bath was 3,020.degree. F.
A refining slag, consisting of 2,500 lbs of burnt lime, 300 lbs of
fluorspar and 250 lbs of 50 percent ferrosilicon, was then added to
the vessel; and the vessel was rotated to the vertical position and
stirred with argon to fuse the slag. The refining slag was added to
further reduce the sulfur content of the metal. After thoroughly
exposing the metal to the refining slag, the vessel was again
tilted and 1,380 lbs of electrolytic manganese was added to bring
the metal within the specifications. The bath temperature was again
measured and found to be 2,930.degree. F and the vessel was further
stirred with argon to insure that the manganese addition was
uniformly distributed. The vessel was then tilted again and
deslagged, rotated to the vertical position, covered and evacuated
to aid in decreasing the temperature of the bath and finally tapped
into a teeming ladle. The final chemistry of the metal was found to
be 0.007 percent carbon, 1.58 percent managanese, 0.03 percent
phosphorus, 0.009 percent sulfur, 18.32 percent chromium, 9.28
percent nickel and 0.48 percent silicon.
Throughout the entire blow, the slag remained fluid and as is
evident from the data herein, the loss of chromium to the slag
phase was minimal.
* * * * *