U.S. patent number 3,871,872 [Application Number 05/365,310] was granted by the patent office on 1975-03-18 for method for promoting metallurgical reactions in molten metal.
This patent grant is currently assigned to Union Carbide Corporation. Invention is credited to James H. Downing, Robert H. Kaiser.
United States Patent |
3,871,872 |
Downing , et al. |
March 18, 1975 |
METHOD FOR PROMOTING METALLURGICAL REACTIONS IN MOLTEN METAL
Abstract
Method and apparatus for promoting metallurgical reactions in
molten metal employing high speed stirring.
Inventors: |
Downing; James H. (Clarence,
NY), Kaiser; Robert H. (Youngstown, NY) |
Assignee: |
Union Carbide Corporation (New
York, NY)
|
Family
ID: |
23438347 |
Appl.
No.: |
05/365,310 |
Filed: |
May 30, 1973 |
Current U.S.
Class: |
420/578; 266/235;
75/583; 420/85; 423/348; 420/117 |
Current CPC
Class: |
F27D
27/00 (20130101); C01B 33/037 (20130101); C22B
9/00 (20130101); C21C 7/076 (20130101); Y02P
10/20 (20151101) |
Current International
Class: |
C21C
7/076 (20060101); C21C 7/04 (20060101); F27D
23/04 (20060101); C01B 33/037 (20060101); F27D
23/00 (20060101); C01B 33/00 (20060101); C22B
9/00 (20060101); C21c 007/00 () |
Field of
Search: |
;75/61,93R,129
;423/350,348,349 ;266/34A |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Cervinka et al., Brutcher Trans. No. 7892, from Hutnicke Listy,
Vol. 20, 1965, No. 6, pp. 394-400..
|
Primary Examiner: Rutledge; L. Dewayne
Assistant Examiner: Andrews; M. J.
Attorney, Agent or Firm: McCarthy; Frederick J.
Claims
What is claimed is:
1. A method for refining molten metal containing impurities which
comprises
i. introducing molten metal into a substantially cylindrically
shaped vessel
ii. agitating the molten metal in said vessel by means of a
graphite rotating agitating member substantially centrally and
axially aligned within said vessel with the bottom portion of said
agitating member being in the upper 50 percent of the height of the
metal bath, said agitating member being rotated at a speed of from
about 120 to 225 r.p.m. to provide turbulent agitation at least at
the surface of the metal bath and said agitating member comprising
a substantially cylindrical hub portion having from three to eight
radial extensions, the length of said radial extensions being from
about 25 to 85 percent of the diameter of the hub, the width of
said radial extensions being about 40 to 80 percent of their
length, and the height of said radial extensions being from about
75 to 200 percent of the hub diameter and the diameter of a circle
circumscribing said radial extensions being about 25 to 40 percent
of the diameter of said vessel containing said molten metal.
2. A method in accordance with claim 1 wherein the surface of the
agitating member is provided with a thin adherent coating
consisting essentially of about 45 t0 70% SiO.sub.2, 10 to 35% CaO,
up to 30% MgO, and up to 15% Al.sub.2 O.sub.3.
3. A method in accordance with claim 1 wherein the molten metal
contains at least 50 percent silicon and calcium and aluminum
impurities and wherein a slag is introduced into the molten metal
containing vessel, said slag consisting essentially of about 45 to
70% SiO.sub.2, 10-35% CaO, 9-30% MgO.
Description
The present invention is directed to an apparatus and method for
promoting metallurgical reactions. More particularly, the present
invention is directed to a method and apparatus whereby molten
metal is agitated in such a manner as to efficiently expose the
molten metal to solid, gaseous, or liquid reactants so as to
rapidly complete metallurgical reactions with the molten metal.
It is an important industrial practice to react molten metal
product with various substances to alter the chemical composition
of the molten metal in order to obtain a final desired composition.
For example, gases, such as air, oxygen, and chlorine, have been
introduced into molten ferrosilicon baths for the purpose of
reducing the calcium and aluminum contents thereof. These practices
have been effective but have had the disadvantage in some cases of
undesirably chilling the molten metal bath and of requiring
relatively long processing times and relatively expensive process
equipment.
It has also been proposed to stir molten metal with various
apparatus such as described in U.S. Pat. Nos. 3,664,826 and
3,592,629 to promote metallurgical reactions. The practices
disclosed in the afore-mentioned patents require either complicated
mechanical stirring equipment or close control of stirring patterns
in the molten metal.
It is therefore an object of the present invention to provide an
uncomplicated process and apparatus for promoting and rapidly
completing metallurgical reactions involving molten metal.
Other objects will be apparent from the following description and
claims taken in conjunction with the drawing wherein
FIG. 1 shows an elevational view of an apparatus in accordance with
the present invention,
FIGS. 2 and 3 show a plan and elevational view of the agitating
mechanism of the apparatus of the present invention and
FIG. 4 shows a fragmented peripheral portion of the agitating
mechanism of the apparatus of the present invention having a
protective coating in accordance with the present invention.
The present invention can be illustrated in connection with the
drawing wherein a conventional ladle is indicated in FIG. 1 at 10
having an iron shell 12 and a refractory lining 14. The molten
metal to be treated, indicated at 16, is held in the ladle 10 and
an agitating member 18 is immersed in the molten metal. The
material composition of the agitating member and its configuration
are important in the practice of the present invention. The
agitating member 18 is machined from graphite to the shape as shown
in FIGS. 2 and 3, more fully described herein below.
Agitating member 18, machined from high-density graphite, can be
provided at its metal contacting surfaces with a thin adherent
coating layer 17 of silica based slag formed from contact of the
graphite surfaces with a molten mixture of silica, lime, alumina,
and magnesia. The slag for this purpose consists essentially of
about 45 to 70 percent by weight SiO.sub.2, 10 to 35% CaO, up to
30% MgO and up to 15% Al.sub.2 O.sub.3. In the case of aluminum and
calcium removal from silicon or silicon-base alloys with the aid of
a molten synthetic slag as hereinafter described, treatment with
such slag will provide the desired coating. It has been observed
that the portion of the agitating member 18, and the portion of
supporting shaft 34, which were immersed in the molten metal and
slag and had an adherent coating did not suffer appreciable
oxidation whereas the portion of shaft 34 which was not so immersed
showed oxidation attack which led to ultimate failure. The slag
layer 17 is typically on the order of 0.03-2.5 mm. in thickness.
This thickness can be obtained by immersing the graphite member 18
in the molten slag for about one minute or more. As long as the
slag is molten the temperature is not critical.
The configuration of the agitating device 18 is also important in
the practice of the present invention. With reference to FIGS. 2
and 3, the graphite agitating member comprises a hub portion 20
having from three to eight and preferably six substantially
identical radial extensions 22 having a length of from about 25 to
about 85 percent of the diameter of hub portion 20. The average
width of the extension 22 is about 40 to 80 percent of their
length. The height of agitating member 18, indicated at 24, is from
about 75 to 200 percent of its hub diameter. It has been found that
the foregoing configuration is important, together with the
abovementioned adherent coating in the high speed agitation
practice of the present invention.
For example, in the practice of the present invention high rotation
speeds are employed to rapidly complete the metallurgical reactions
involved thus avoiding long operating times and undesired chilling
of the bath. The configuration of the agitating member of the
present invention can accommodate the high mechanical stresses
involved with high rotation speeds while providing a high order of
turbulence. It has been found that the coating previously described
is remarkably adherent to the graphite agitating member and its
thickness remains essentially constant during operation in which a
silica-base slag is employed and in which calcium and aluminum
impurities are being removed. The reason for this is not fully
understood but may be due to the renewal of the coating by the slag
constituents present. In the case when a silica base slag is not
being used, or calcium and aluminum are not being removed by
oxidation, it may be desirable to periodically recoat the agitation
member with silica base slag as described herein.
With further reference to FIG. 1, agitating member 18 is
constructed so that it outside diameter 26 is from about 25-40
percent of the average diameter of the metal bath indicated at 28.
Also, agitating member 18 is arranged so that it is immersed in the
molten metal bath with the bottom portion thereof located in the
upper 50 percent of height of the metal bath. With agitating member
18 arranged as indicated, and with reference to FIG. 1 of the
drawing, motor 30 acting through speed reducer 32 and clamp 33
drives shaft 34 and hence agitating member 18 at a speed of from
about 120 to 225 rpm. At rotation speeds as specified, and with the
agitating member configured as indicated, the metal bath is
vigorously and turbulently agitated. A rotation speed of at least
about 120 rpm is important to enable rapid completion of the
metallurgical reaction involved; rotation speeds above about 225
rpm result in excessive splashing and possible loss of metal. When
the molten metal to be treated is a silicon containing alloy and it
is desired to remove calcium and aluminum impurities, the exposure
of the molten metal to the surrounding air provided by the
above-mentioned agitation is sufficient to rapidly reduce the
calcium content from about 0.20 to 0.02 percent and the aluminum
content from about 0.5 to 0.3 percent in less than 8 minutes. For
such operations, the agitating member is preferably located in the
upper 10 percent of the molten bath. In instances where solid metal
additions are to be added to the molten metal, e.g., finely
particulated ferrosilicon is added to a ferrosilicon metal bath,
the agitating member is preferably in the upper 20 to 40 percent of
the metal bath.
In instances where aluminum and calcium impurities are to be
removed from silicon or ferrosilicon using a synthetic slag, the
agitating member is preferably in the upper 10-20 percent of the
metal bath. As illustrated, motor 30 and speed reducer 32 are
supported on refractory protected support member 29 which can be
raised and lowered by hydraulic pistons 35 to adjust the position
of agitating member 18.
Particular advantages of the present invention is the rapidity
obtained for the metallurgical reactions involved and the long life
of the agitating member. The rapidity of the reactions avoids the
undesirable effects which can occur on account of cooling of the
melt during prolonged agitation.
The following examples will further illustrate the present
invention.
EXAMPLE I
5970 lb. of 75% FeSi having a composition of 0.54% Al and 0.22% Ca
were placed in a ladle having an average inner diameter of 4.1 feet
to a depth of 2.8 feet. The initial temperature of the metal was
1510.degree.C. A graphite agitating member of the type shown in the
drawing having a hub diameter of 8 inches and a height of 8 inches
and six extensions having an average thickness of 21/2 inches was
immersed in the molten metal with the bottom thereof about 10
inches below the surface. A blended mixture of 105 lb. lime, 200
lb. sand, and 32 lb. magnesia was added to the ladle. The agitating
member was rotated at 120 rpm for 25 minutes. The metal was tapped
from the ladle and analyzed 0.07% Al and 0.04% Ca.
EXAMPLE II
8725 lb. of 50% FeSi having a composition of 0.60% Al and 0.07% Ca
were placed in a ladle having an average inner diameter of 4.1 feet
to a depth of 3.0 feet. The initial temperature of the metal was
1600.degree.C. A graphite agitating member of the type shown in the
drawing having a hub diameter of 8 inches and a height of 8 inches
and six extensions having an average thickness of 21/2 inches was
immersed in the molten metal with the bottom thereof about 11
inches below the surface. A blended mixture of 100 lb. lime, 200
lb. sand and 45 lb. magnesia was added to the ladle. The agitating
member was rotated at 120 rpm for 30 minutes. The metal was tapped
from the ladle and analyzed 0.05% Al and 0.04% Ca.
EXAMPLE III
23,980, lb. of 50% FeSi having a composition of 0.91% Al and 0.26%
Ca were placed in a ladle having an average inner diameter of 5.0
feet to a depth of 4.7 feet. The initial temperature of the metal
was 1477.degree.C. A graphite agitating member of the type shown in
the drawing having a hub diameter of 8 inches and a height of 8
inches and six extensions having an average thickness of 21/2
inches was immersed in the molten metal with the bottom thereof
about 12 inches below the surface. A blended mixture of 492 lb.
lime, 800 lb. sand, and 250 lb. magnesia was added to the ladle.
The agitating member was rotated at 175 rpm for 21 minutes. The
metal was tapped from the ladle and analyzed 0.08% Al and 0.01%
Ca.
EXAMPLE IV
3990 lb. of silicon having a composition of 0.54% Al and 0.20% Ca
were placed in a ladle having an average inner diameter of 3.4 feet
to a depth of 2.7 feet. The initial temperature of the metal was
1430.degree.C. A graphite agitating member of the type shown in the
drawing having a hub diameter of 8 inches and a height of 8 inches
and six extensions having an average thickness of 21/2 inches was
immersed in the molten metal with the bottom thereof 8 inches below
at the surface. The agitating member was rotated at 120 rpm for 7
minutes. The metal was tapped from the ladle and analyzed 0.22% Al
and 0.01% Ca.
EXAMPLE V
3665 lb. of silicon having a composition of 0.79% Al and 0.12% Ca
were placed in a ladle having an average inner diameter of 3.3 feet
to a depth of 2.6 feet. The initial temperature of the metal was
1500.degree.C. A graphite agitating member of the type shown in the
drawing having a hub diameter of 8 inches and a height of 8 inches
and six extensions having an average thickness of 21/2 inches was
immersed in the molten metal with the bottom thereof about 12
inches below the surface. A blended mixture of 76 lb. lime, 146 lb.
sand, and 31 lb. magnesia was added to the ladle. The agitating
member was rotated at 150 rpm for 15 minutes. The metal was tapped
from the ladle and analyzed 0.08% Al and 0.01% Ca.
EXAMPLE VI
22,450 lb. of 50% FeSi were placed in a ladle having an average
inner diameter of 5.0 feet to a depth of 4.6 feet. The intial
temperature of the metal was 1521.degree.C. A graphite agitating
member of the type shown in the drawing having a hub diameter of 8
inches and a height of 8 inches and six extensions having an
average thickness of 21/2 inches was immersed in the molten metal
with the bottom thereof about 16 inches below the surface. 1150 lb.
of fine particulated 50% FeSi were added to the ladle. The
agitating member was rotated at 145 rpm for 11 minutes. The
particulated metal was thoroughly melted by the bulk metal.
In the practice of the present invention, calcium and aluminum
impurities can be rapidly removed from molten silicon and alloys
containing about 50 percent or more silicon, e.g., the various
ferrosilicon alloys with the use of a synthetic slag of the
following composition
45 - 70% SiO.sub.2 10 - 35% CaO 9 - 30% MgO
The amount of slag with respect to molten metal is from about 3.5
to 9 percent of the weight of the metal bath with higher amounts of
slag in this range being employed with higher silicon contents in
the metal being treated. With the use of the aforementioned range
of slag, lowering of the aluminum impurity level to 0.1 percent can
be achieved. If higher aluminum levels can be tolerated lesser
amounts of slag can be used.
The present invention may also be utilized in a wide variety of
metal treatments such as additions of calcium carbide to iron for
purposes of desulphurization, the dissolving of metal additions in
molten metal, and in lowering the total carbon content of
silicon-manganese alloys, e.g., silico-manganese using by-product
slag with the molten metal.
* * * * *