US3203883A - Method of refining molten metals by electrolyzing molten slag under arc discharge - Google Patents

Method of refining molten metals by electrolyzing molten slag under arc discharge Download PDF

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Publication number
US3203883A
US3203883A US177884A US17788462A US3203883A US 3203883 A US3203883 A US 3203883A US 177884 A US177884 A US 177884A US 17788462 A US17788462 A US 17788462A US 3203883 A US3203883 A US 3203883A
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United States
Prior art keywords
refining
molten
slag
metal
arc discharge
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US177884A
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English (en)
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Ototani Tohei
Maruyama Masuteru
Matsumoto Jiro
Izumi Sumio
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RCSEARCH INST FOR IRON STEEL A
RCSEARCH INSTITUTE FOR IRON STEEL AND OTHER METALS OF TOHOKU UNIVERSITY
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RCSEARCH INST FOR IRON STEEL A
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/52—Manufacture of steel in electric furnaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0075—Treating in a ladle furnace, e.g. up-/reheating of molten steel within the ladle
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/076—Use of slags or fluxes as treating agents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16—Remelting metals
    • C22B9/18—Electroslag remelting
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method of refining molten metals by electrolyzing molten slag under are discharge at ambient pressure characterized in that molten slag consisting of calcium silicate containing one or more of halides of alkaline earth metals, or in addition therewith aluminum oxides or aluminum halides is used as the electrolyte and electrolyzed by applying direct current high potential between the molten metal as a cathode and an anode suspended above the electrolyte, thereby effecting deoxidation of the molten metal.
  • the principal object of the invention is to effect strong refining of steels, pig irons, ferro-alloys and non-ferrous metals in the molten state and more patrieularly to efiect intensitive deoxidizing refining.
  • the electrolytic refining by high potential arc discharge of the invention has the following specialities if compared with an ordinary electrolysis using dipped electrode wherein an anode is dipped into the electrolyte and the electrolysis is carried out at a comparatively low voltage.
  • the temperature of molten slag, molten metal or alloy during the electrolytic refining can be easily maintained by the heat of arc.
  • the fluidity of the molten slag can be maintained at a suitable degree.
  • the temperature of the molten metal can be easily maintained by the heat of arc and the powerful reduction refining which has heretofore been considered difiicult is rendered possible so that it can be applied to the production of steel, and moreover, the time required for the reduction is made substantially equal to that of ordinary processes or can be shortened even less than that. Accordingly, the cost of melting refining in the electrolytic refining under high potential arc discharge is substantially same as that of melting refining in ordinary refining method and the cost of the direct current electrolyzing device can be compensated by the improvement in the yield of the product.
  • a large merit obtainable in carrying out the method of the invention is to produce a melt of refined metals due to the extreme deoxidation and desulfurization for eliminating impurities and improving the yield of the product and its .limit varies according to the kinds of metals, yet the deoxidation as described hereafter by an example results in 20 to 60% improvement compared with ordinary refining and the yield is improved for 1 to 4%.
  • the deoxidation and desulfurization mechanism of the electrolytic refining using arc discharge is as follows:
  • the reaction of electrolytic refining of the molten slag proceeds 1) by the electrochemical reaction and (2) thermo-dynamic reaction.
  • Electrochemical reacti0n.2CaO'SiO and CaX are taken as a slag to be deoxidized and desulfurized for example.
  • thermo-dynamic reaction (1) T hermo-dynamic reaction.-Assuming the activities of S and Fe in the molten iron be expressed by aS and aFe respectively and the activities of 8 and Fe in the molten slag be aS and 'aFe respectively and the equilibrium constant between them be L S, then the following thermo-dynamic relation is established.
  • both of aS and aFe are reduced by the reaction between two poles and accordingly, in order to maintain the equilibrium, FeS in the molten iron must proceed into the molten slag to efiect the deoxidation refining reaction simultaneously to the desulfurization.
  • the reaction occurs on the surface of the molten metal (interface between the molten slag) the reaction product (alumina) is consumed by the molten slag at once so that it cannot be retained in the molten metal as non-metallic inclusions and refined metal may be obtained.
  • the excessive precipitated aluminum serves to produce fine grained structure and to toughen the steel entering into the steel in case of refining.
  • FIG. 1 is a diagrammatic sectional view of low voltage dipped electrode electrolytic device
  • FIG. 2 is a similar diagrammatic sectional view to FIG. 1 illustrating the location of an anode in a high potential are discharge electrolytic refining device.
  • Example 1 In stainless steels containing 0.16% C and 13% Cr, the comparison of ordinary refining, low potential dipped electrode electrolysis and are discharge electrolysis is shown in the following table:
  • the furnace used is 1 ton Hroult type electrolytic furnace.
  • Example 2 In low carbon steels, such as stainless steel containing less than 0.12% C and 13% Cr, even if very low carbon materials are used as charging raw material the carbon content of the molten steel becomes higher than 0.15% in the low voltage dipped electrode electrolysis so that the electrolysis under high voltage are discharge must be used necessarily and the result is as shown in the following:
  • the furnace used is 1 ton Hroult type electrolytic furnace.
  • Example 3 Fromthe results of test carried out similarly to cast iron, high voltage are discharge electrolysis is not only smoothly carried out its operation if compared with low voltage dipped electrode electrolysis but also the effect of deoxidation and desulfurization are increased. So that the nodularization of graphite due to inoculation can be made easy.
  • the furnace used is 1 ton Hroult type electrolytic furnace.
  • Example 4 The next table illustrates an example of the method of the invention as applied to pure copper. It is apparent that the pure copper of very high quality (oxygen free copper) was obtained.
  • the furnace used was kg. high frequency electrolytic furnace.
  • Example 5 Iron-chromium alloys and Fe-Si alloy are subjected to the high potential are discharge electrolytic refining and as its results the oxygen content in the alloy was slag by are discharge and to effect electro-chemical dcoxidation and desulphurization refining.
  • a method of are discharge electrolytic refining of a molten metal, wherein said metal is selected from the f steel cast iron ferro-alloys and coprcdueed to $6 to $6 and when the refined alloy ts used 5 group .mslsung 2 for the melting of iron and steel, refined steel and iron which compnsc.s f f metal be refined comainingkss oxygen was obtained.
  • the extent of the deoxidation refining according to the pound sflcctcd from group cons'slmg of compqunds method of the invention depends on the kinds of metals of alkali metals, alkaline earth metals, tron and aluminum and in higher alloy steels it is sometimes better than 10 5 an elcctmlye above surface of smd slag suspeng' vacuum smcmng. mg an anode and applying a D.C.
  • the present method has advantages and metal be refined at f pressure that if compared with ordinary method of smelting the to clcctmlyu the 5.138 are dlscharge p products of high purity can be obtain at the Sam: or effect electrochemical deoxldatton and desulphurization less costs owing to the extremely strong deoxidation. 15 mfimng' What we claim is: References Cited by the Examiner 1.
  • a method of arc-discharge, clCCtrolytic X'Cfining Of a molten metal wherein said metal is selected from the group consisting of steel, cast iron, terroalloys, and cop- 800'984 10/05 Chance 204-140 per, which comprises covering said metal to be refined 2,787,592 4/ 57 Burkhal'dl 204- with a molten calcium silicate slag containing a compound selected from the group consisting of compounds of alkali metals, alkaline earth metals, iron and aluminum as an electrolyte, above the surface of said slag, suspending an anode and applying a D.C. voltage between said anode and said metal to be refined to electrolyze the molten FOREIGN PATENTS 741,567 12/55 Great Britain.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
US177884A 1961-07-01 1962-03-06 Method of refining molten metals by electrolyzing molten slag under arc discharge Expired - Lifetime US3203883A (en)

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DE (1) DE1608738B1 (da)
GB (1) GB994378A (da)
SE (1) SE318117B (da)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4246023A (en) * 1977-07-01 1981-01-20 Dso "Charna Metalurgia" Method and apparatus for the refining of iron-based melts
FR2517328A1 (fr) * 1981-12-01 1983-06-03 Iso Metalurgkomplekt Procede et dispositif pour le traitement et l'affinage d'alliages metalliques liquides par chauffage a l'arc electrique a courant continu
WO1988009388A1 (en) * 1987-05-26 1988-12-01 The University Of Toronto Innovations Foundation Process for treating liquid metals
US4875985A (en) * 1988-10-14 1989-10-24 Brunswick Corporation Method and appparatus for producing titanium
US4964973A (en) * 1988-10-14 1990-10-23 Brunswick Corporation Method and apparatus for producing titanium
WO1993017132A1 (en) * 1992-02-28 1993-09-02 Massachusetts Institute Of Technology Process for improving metal production in iron and steelmaking processes
WO1996022395A1 (en) * 1995-01-20 1996-07-25 Massachusetts Institute Of Technology Method for enhancing reaction rates in metals refining, extraction, and recycling operations involving melts containing ionic species such as slags, mattes, fluxes and the like
WO1997016572A1 (en) * 1995-10-30 1997-05-09 Massachusetts Institute Of Technology Accelerated decarburization of iron-carbon melts
US20070215483A1 (en) * 2006-03-10 2007-09-20 Elkem As Method for electrolytic production and refining of metals
WO2007106709A3 (en) * 2006-03-10 2007-11-29 Elkem As Method for electrolytic production and refining of metals
WO2009028924A1 (es) * 2007-08-29 2009-03-05 Jack Victor Nyrup Aguilar Compuesto ionizante estabilizador del arco eléctrico
CN101658901A (zh) * 2008-03-10 2010-03-03 王宇新 避免球铁铁液在浇注过程中发生球化衰退和降低浇注温度的处理方法及专用浇注设备
US20130228469A1 (en) * 2010-11-02 2013-09-05 I'msep Co., Ltd. Production method for metal microparticle
CN105385857A (zh) * 2015-11-06 2016-03-09 攀钢集团成都钢钒有限公司 防增p电渣锭重熔用渣的冶炼方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2396087A1 (fr) * 1977-09-02 1979-01-26 Tscherna Metalurgia Procede et dispositif pour le raffinage de masses fondues a base de fer
SE461048B (sv) * 1987-03-02 1989-12-18 Gyproc Ab Perforerad, ljudabsorberande skiva

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US800984A (en) * 1905-06-02 1905-10-03 Henry M Chance Process of purifying metals.
GB741567A (en) * 1952-01-10 1955-12-07 Guszstahlwerk Bochumer Ver Ag A method of making high-grade steel
US2787592A (en) * 1948-10-01 1957-04-02 Ver Deutsche Metallwerke Ag Method for the treatment of metal

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US800984A (en) * 1905-06-02 1905-10-03 Henry M Chance Process of purifying metals.
US2787592A (en) * 1948-10-01 1957-04-02 Ver Deutsche Metallwerke Ag Method for the treatment of metal
GB741567A (en) * 1952-01-10 1955-12-07 Guszstahlwerk Bochumer Ver Ag A method of making high-grade steel

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4246023A (en) * 1977-07-01 1981-01-20 Dso "Charna Metalurgia" Method and apparatus for the refining of iron-based melts
FR2517328A1 (fr) * 1981-12-01 1983-06-03 Iso Metalurgkomplekt Procede et dispositif pour le traitement et l'affinage d'alliages metalliques liquides par chauffage a l'arc electrique a courant continu
US4462878A (en) * 1981-12-01 1984-07-31 Iso "Metalurgkomplekt" Method of treating and refining liquid metal alloys by direct current electric arc heating
WO1988009388A1 (en) * 1987-05-26 1988-12-01 The University Of Toronto Innovations Foundation Process for treating liquid metals
JPH03500304A (ja) * 1987-05-26 1991-01-24 ユニバーシティ・オブ・トロント・イノベーションズ・ファウンデーション 液状金属の処理方法
US4875985A (en) * 1988-10-14 1989-10-24 Brunswick Corporation Method and appparatus for producing titanium
WO1990004043A3 (en) * 1988-10-14 1990-05-03 Brunswick Corp Method of producing titanium
US4964973A (en) * 1988-10-14 1990-10-23 Brunswick Corporation Method and apparatus for producing titanium
WO1993017132A1 (en) * 1992-02-28 1993-09-02 Massachusetts Institute Of Technology Process for improving metal production in iron and steelmaking processes
WO1996022395A1 (en) * 1995-01-20 1996-07-25 Massachusetts Institute Of Technology Method for enhancing reaction rates in metals refining, extraction, and recycling operations involving melts containing ionic species such as slags, mattes, fluxes and the like
US5700308A (en) * 1995-01-20 1997-12-23 Massachusetts Institute Of Technology Method for enhancing reaction rates in metals refining extraction, and recycling operations involving melts containing ionic species such as slags, mattes, fluxes
WO1997016572A1 (en) * 1995-10-30 1997-05-09 Massachusetts Institute Of Technology Accelerated decarburization of iron-carbon melts
US20070215483A1 (en) * 2006-03-10 2007-09-20 Elkem As Method for electrolytic production and refining of metals
WO2007106709A3 (en) * 2006-03-10 2007-11-29 Elkem As Method for electrolytic production and refining of metals
JP2009529607A (ja) * 2006-03-10 2009-08-20 エルケム アクシエセルスカプ 金属の電解製造及び精練方法
AU2007226754B2 (en) * 2006-03-10 2011-01-20 Elkem As Method for electrolytic production and refining of metals
US7901561B2 (en) 2006-03-10 2011-03-08 Elkem As Method for electrolytic production and refining of metals
WO2009028924A1 (es) * 2007-08-29 2009-03-05 Jack Victor Nyrup Aguilar Compuesto ionizante estabilizador del arco eléctrico
CN101658901A (zh) * 2008-03-10 2010-03-03 王宇新 避免球铁铁液在浇注过程中发生球化衰退和降低浇注温度的处理方法及专用浇注设备
US20110005351A1 (en) * 2008-03-10 2011-01-13 Yuxin Wang Method for treating spheroidal graphite iron and pouring device thereof
US8419821B2 (en) * 2008-03-10 2013-04-16 Yuxin Wang Method for treating spheroidal graphite iron and pouring device thereof
US8767793B2 (en) 2008-03-10 2014-07-01 Yuxin Wang Method for treating spheroidal graphite iron and pouring device thereof
US20130228469A1 (en) * 2010-11-02 2013-09-05 I'msep Co., Ltd. Production method for metal microparticle
US9562296B2 (en) * 2010-11-02 2017-02-07 I'msep Co., Ltd. Production method for silicon nanoparticles
CN105385857A (zh) * 2015-11-06 2016-03-09 攀钢集团成都钢钒有限公司 防增p电渣锭重熔用渣的冶炼方法

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DE1608738B1 (de) 1972-01-05
SE318117B (da) 1969-12-01
GB994378A (en) 1965-06-10

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