US3871872A - Method for promoting metallurgical reactions in molten metal - Google Patents

Method for promoting metallurgical reactions in molten metal Download PDF

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US3871872A
US3871872A US365310A US36531073A US3871872A US 3871872 A US3871872 A US 3871872A US 365310 A US365310 A US 365310A US 36531073 A US36531073 A US 36531073A US 3871872 A US3871872 A US 3871872A
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molten metal
percent
agitating member
diameter
metal
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US365310A
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James H Downing
Robert H Kaiser
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ELKEM METALS COMPANY A NEW YORK GENERAL PARTNERSHIP
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Union Carbide Corp
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Assigned to ELKEM METALS COMPANY, A NEW YORK GENERAL PARTNERSHIP reassignment ELKEM METALS COMPANY, A NEW YORK GENERAL PARTNERSHIP ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: UNION CARBIDE CORPORATION, A NY CORP.
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27DDETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D27/00Stirring devices for molten material
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/02Silicon
    • C01B33/037Purification
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04Removing impurities by adding a treating agent
    • C21C7/076Use of slags or fluxes as treating agents
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Process efficiency
    • Y02P10/21Process efficiency by recovering materials
    • Y02P10/242Slag reuse in metallurgical processes

Abstract

Method and apparatus for promoting metallurgical reactions in molten metal employing high speed stirring.

Description

United States Patent Downing et al.

METHOD FOR PROMOTING 1 1' Mar. 18, 1975 References Cited UNITED STATES PATENTS METALLURGICAL REACTIONS IN [56] MOLTEN METAL Inventors: James H. Downing, Clarence; 3,743,263

Robert H. Kaiser, Youngstown,

7/1973 Szekely 266/34 A OTHER PUBLICATIONS Cervinka et al., Brutcher Trans. No. 7892, from Hutboth of NY.

Assignee: Union Carbide Corporation, New

York, NY.

Filed: May 30, 1973 nicke Listy, Vol. 20, 1965, No. 6, pp. 394-400.

Primary Examiner-L. Dewayne Rutledge Assistant Examiner-M. J. Andrews Appl. No.: 365,310

US. Cl 75/61, 75/93 R, 75/129, 266/34 A, 423/348 Int. Cl. C2lc 7/00 Field of Search 75/61, 93 R, 129; 423/350, 423/348, 349; 266/34 A Method and apparatus forpromoting metallurgical reactions in molten metal employing high speed stirring.

Attorney, Agent, or Firm-Frederick J. McCarthy ABSTRACT 3 Claims, 4 Drawing Figures 1 METHOD FOR PROMOTING METALLURGICAL REACTIONS IN MOLTEN METAL The present invention is directed to an apparatus and I 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 7 into-molten ferrosilicon baths for the purpose of reduc-,

ing 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 US. 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,

F168. 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 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 thegraphite 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 10 to 35% CaO, up to 30% MgO and up to M 0 In the case of aluminum and calcium removal from silicon or siliconbase 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 ,i te 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 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 withthe 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 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 abovementioned 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 l-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% Aland 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 1510C. 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 2 /2 inches was immersed in the molten metal with the bottom thereof about 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% Aland 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 1600C. 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 2 /2 inches was immersed in the molten metal with the bottom thereof about 1 1 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 1477C. A graphite agitating member of the type shown in the drawing having a hub diameter of 8 inches and a height EXAMPLE IV 3990lb. 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 l430C. A graphite agitating member of the type shown in the drawing having a hub diameter of 8 inches and a height of 8 inches I and six extensions having an average thickness of 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

I 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 1500C. 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 2 /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 l52lC. A graphite agitating member of thetype 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 2 /2 inches was immersed in the molten metal with the bottom thereof about 16 inches below the surface. 1 150 lb. of fine particulated 50% FeSi were added to the ladle. The agitating member was rotated at rpm for l 1 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 10-35% CaO 9-307. 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. What is claimed is: l. 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 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 ofsaid 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 10 to 35% CaO, up to 30% MgO. and up to of a graphite rotating agitating member substantially centrally and axially aligned within saidvessel 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 rpm. to provide turbulent agitation at least at the surface of the

Claims (3)

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 EXTENSION,THE LENGTH OF SAID RACIAL 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 RIDIAL 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% SiO2, 10 to 35% CaO, up to 30% MgO, and up to 15% Al2O3.
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% SiO2, 10-35% CaO, 9-30% MgO.
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US4063932A (en) * 1974-07-17 1977-12-20 Union Carbide Corporation Method for admixing solids in molten metal
US4094731A (en) * 1976-06-21 1978-06-13 Interlake, Inc. Method of purifying silicon
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US4151264A (en) * 1977-02-14 1979-04-24 Wacker-Chemie Gmbh Process of melting down and purifying silicon
EP0002135A1 (en) * 1977-11-21 1979-05-30 Union Carbide Corporation Improved refined metallurgical silicon and process for the production thereof
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US4195067A (en) * 1977-11-21 1980-03-25 Union Carbide Corporation Process for the production of refined metallurgical silicon
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Cited By (132)

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Publication number Priority date Publication date Assignee Title
US4063932A (en) * 1974-07-17 1977-12-20 Union Carbide Corporation Method for admixing solids in molten metal
US4046559A (en) * 1976-02-23 1977-09-06 Kennecott Copper Corporation Pyrometallurgical system for liquid-liquid contacting
US4094731A (en) * 1976-06-21 1978-06-13 Interlake, Inc. Method of purifying silicon
US4151264A (en) * 1977-02-14 1979-04-24 Wacker-Chemie Gmbh Process of melting down and purifying silicon
US4193974A (en) * 1977-11-21 1980-03-18 Union Carbide Corporation Process for producing refined metallurgical silicon ribbon
US4124410A (en) * 1977-11-21 1978-11-07 Union Carbide Corporation Silicon solar cells with low-cost substrates
EP0002135A1 (en) * 1977-11-21 1979-05-30 Union Carbide Corporation Improved refined metallurgical silicon and process for the production thereof
US4193975A (en) * 1977-11-21 1980-03-18 Union Carbide Corporation Process for the production of improved refined metallurgical silicon
US4195067A (en) * 1977-11-21 1980-03-25 Union Carbide Corporation Process for the production of refined metallurgical silicon
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