WO1994019496A1 - Composite metallurgique/d'isolation et son procede de fabrication - Google Patents

Composite metallurgique/d'isolation et son procede de fabrication Download PDF

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Publication number
WO1994019496A1
WO1994019496A1 PCT/AU1994/000083 AU9400083W WO9419496A1 WO 1994019496 A1 WO1994019496 A1 WO 1994019496A1 AU 9400083 W AU9400083 W AU 9400083W WO 9419496 A1 WO9419496 A1 WO 9419496A1
Authority
WO
WIPO (PCT)
Prior art keywords
composite
calcium
metallurgical
magnesium
insulating
Prior art date
Application number
PCT/AU1994/000083
Other languages
English (en)
Inventor
Milena Maric
Eric Pye
Original Assignee
Laporte Group Australia Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Laporte Group Australia Limited filed Critical Laporte Group Australia Limited
Priority to AU61773/94A priority Critical patent/AU6177394A/en
Publication of WO1994019496A1 publication Critical patent/WO1994019496A1/fr

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Classifications

    • 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
    • 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
    • C21C7/0087—Treatment of slags covering the steel bath, e.g. for separating slag from the molten metal
    • 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

  • This invention relates to insulating and/or metallurgical composites, and in particular to composites which are utilised as fluxes in pelletised or granular form for iron and steel manufacture.
  • the cover can perform a number of functions, ranging from one extreme of purely acting as a insulating flux, to the other extreme of purely acting as a metallurgical flux, or, an intermediate function of simultaneously acting as an insulating and a metallurgical flux.
  • an insulating flux is to minimise the heat loss, through radiation, from the surface of a ferrous melt.
  • an insulating flux must readily spread over the melt surface, remain predominantly in a solid form, (ie. powder/pellet form, a non-liquid) at 1500 to 1800°C and not react adversely with the ferrous melt or furnace refractory.
  • the cover should ideally consist of a thin liquid flux layer (approximate depth 5-30mm) and non liquid layer whose approximate depth is 20-200mm.
  • the liquid flux layer retards re-oxidation of the melt by atmospheric oxygen and the non-liquid layer reduces heat lost (through radiation) from the melt surface.
  • a metallurgical flux The role of a metallurgical flux is to absorb various impurities (such as sulphur, phosphorus, alumina and oxygen), to prevent atmospheric oxidation of a ferrous melt, to modify inclusions whose" presence is detrimental to the properties and processing of ferrous metals etc.
  • Metallurgical flux generally sits on the surface of a ferrous melt and in this application it must form a deep liquid layer at the ferrous melt temperatures.
  • the melting point of a metallurgical flux (low temperature phase) should be within the range of 1100-1400°C.
  • metallurgical flux is comprised of calcium oxide, alumina, silica and magnesium oxide.
  • a metallurgical flux should provide a deep liquid flux layer in contact with the ferrous melt and a non-liquid layer in contact with the liquid flux layer.
  • the liquid layer through turbulent mixing, reacts with the impurities contained in the ferrous melt and thus causes these impurities to be transferred from the ferrous melt to the molten liquid flux layer.
  • the non-liquid layer dissolves into the liquid flux . layer thus replenishing it with active metallurgical components.
  • insulating and metallurgical fluxes have in the past been in very fine powder form.
  • powder forms are undesirable as their use results in a dusty « environment which can cause health and safety problems for plant operators, particularly due to the reactive nature of the powder.
  • the composite pelletised insulant is possible by the use of bentonite (binder) in the range of 15-20%wt where bentonite is-principally used for its binding properties.
  • bentonite significantly reduces the insulating properties of the composite and promotes unfavourable reactions such as intersintering betwen pellets when they are being used, and also lowering of pellet refractoriness. This results in solidification of the flux layer which is undesirable during pouring and handling of molten metal.
  • the composite can be made up of more of the effective components which are required, thus improving the effectiveness of the composite.
  • a composite for providing a metallurgical and/or insulating flux to a molten metal comprising: aluminosilicate material; calcium and/or magnesium bearing material; and, carbonaceous raw material.
  • said aluminosilicate material is selected from one or any combination of: kaolin, flint clay, china clay, calcined flint clay, fly ash, boiler house ash, or molten slags, and/or sillimanite.
  • said calcium and/or magnesium bearing material is selected from one or any combination of: calcium oxide (burnt lime), calcium carbonate, calcium hydroxide, magnesium oxide, dolomite olivine, fosterite and/or vermiculite. - A -
  • saic carbonaceous raw material is selected from any one or combination of: carbon black, coke/graphite and/or exfolliating graphite.
  • the specific reactivity of the flux is varied by addition of raw materials selected from any one or combination of: calcium fluoride, barium fluoride or sodium fluoride, calcium carbide, sodium carbonate, barium oxide, alimina, aluminium or a deoxidising agent similar to aluminium.
  • said composite is provided in the form of pellets, granules, or the like.
  • said composite in pellet, granule or like form is either, placed at the bottom of a tundish or ladle prior to pouring a ferrous melt therein, injected into the melt, and/or, placed into the pouring stream or on top of the molten metal.
  • the proportion of said materials are varied to yield a metallurgical flux composition
  • a metallurgical flux composition comprising: silica (Si0 2 ) 0-50 %wt; alumina (Al-O,) 0-40 %wt; calcium oxide (CaO) 30-70 %wt; calcium carbonate 0-20 %wt; calcium hydroxide (Ca(OH) 2 ) 0-20 %wt; magnesium oxide(MgO) 0-20 %wt; aluminium (Al) 0-10 %wt; carbon (C) 0-10 %wt; calcium cardide 0-5 %wt; calcium fluoride 0-10 %wt; sodium carbonate 0-10 %wt; barium oxide 0-20 %wt.
  • said metallurgical composite in this composition further comprises: binder material, such 'as bentonite, sodium silicate or other binder material 0-15 %wt.
  • binder material such 'as bentonite, sodium silicate or other binder material 0-15 %wt.
  • the metallurgical composite further has insulative properties provided by variation of the proportion of raw materials to yield a metallurgical/ insulative composite, comprising: silica. (Si0 2 ) 5-40 %wt; alumina (A1 2 0 3 ) 0-40 %wt; magnesium/calcium oxide 0-20 %wt; magnesium/calcium carbonate 0-50 %wt; calcium hydroxide 0-50 %wt; carbon (C) 0-36 %wt.
  • the proportion of said materials are varied to yield an insulating composite, comprising: silica (Si0 2 ) 10-70 %wt; alumina (A1 2 0 3 0-50 %wt; calcium oxide (CaO) 0-20 %wt; calcium carbonate 0-20 %wt; calcium hydroxide (Ca(OH) 2 ) 0-20 %wt; carbon (C) 0-26 %wt.
  • said insulating composite in this composition further comprises binder material, such as bentonite, sodium silicate or other binder material in the range 0-15 %wt.
  • binder material such as bentonite, sodium silicate or other binder material in the range 0-15 %wt.
  • the insulation composite further has metallurgical properties provided by variation of the proportion of said materails to produce a metallurgical/ insulating composite, comprising: silica (Si0 2 ) 10-55 %wt; alumina (A1 2 0_) 0-50 %wt; magnesium/calcium oxide 0-20 %wt; magnesium/calcium carbonate 0-50 %wt; calcium hydroxide 0-50 %wt; carbon (C) 0-36 %wt.
  • metallurgical properties provided by variation of the proportion of said materails to produce a metallurgical/ insulating composite, comprising: silica (Si0 2 ) 10-55 %wt; alumina (A1 2 0_) 0-50 %wt; magnesium/calcium oxide 0-20 %wt; magnesium/calcium carbonate 0-50 %wt; calcium hydroxide 0-50 %wt; carbon (C) 0-36 %wt.
  • the proportion of said raw materials are varied to yield a metallurgical/ insulative composite, comprising: silica (Si0 2 ) 5-40 %wt; alumina (A1 2 0 3 ) 0-40 %wt; magnesium oxide/calcium oxide 0-20 %wt; magnesium/calcium carbonate 0-50 %wt; calcium hydroxide 0-50 %wt; carbon (C) 0-36 %wt.
  • the present invention provides processes for manufacturing insulating and/or metallurgical composite in the form of pellets or granules or the like, comprising the steps of: mixing the components in a dry powder form; adding water or other like fluid to the components whilst mixing such that the moisture level is substantially in the range of 15-35%; feeding the resultant moistened mix into a pelletising mill in a controlled manner for formation into pellets; and drying said pellets to remove all the moisture.
  • the present invention provides a process for manufacturing an insulating and/or metallurgical composite, comprising the steps of: (i) briquetting a wet composite; (ii) removing moisture and hardening same; and (iii) crushing the briquette to create granules of predetermined size.
  • the present invention provides a process for manufacturing an insulating and/or metallurgical composite, comprising the steps of: (i) supplying a moist premixed powder, by means of a screw feeder or the like at the base of a hopper onto an inclined rotating disc (or dish) ; (ii) simultaneously supplying fine water sprays to further wet said mix; and
  • one or more of the following characteristics may be varied:
  • composition ranges, together with typical examples thereof, is shown in the following table.
  • the metallurgical flux composition can be achieved by using a mixture of pure components or a mix of pre-melted components such as aluminosilicate or slag and pure components.
  • Magnesium oxide and calcium oxide can be added as pure oxides or as carbonates or as a mixture of oxides, carbonates and hydroxides.
  • composition can be varied in the general range to produce a flux suitable for different processing conditions or for different grades of ferrous melt etc.
  • Further components such as calcium carbide, calcium flouride, barium fluoride, sodium fluoride, sodium carbonate, barium oxide, aluminium and similar deoxidising agents can be added in small quantities to provide fluxes" having different characteristics.
  • a metallurgical composite in the form of pellets or granules has the advantage of being able to be placed in the bottom of a tundish or a ladle before the ferrous melt is poured therein and not create dust (airborn particles) and/or fume when the molten metal is poured on top of it.
  • the purpose of placing a metallurgical flux on the bottom of a ladle or a tundish is to remove impurities from the molten metal (which is poured on top of it); to create a liquid barrier between the molten metal and the ladle/tundish lining; to minimise contaminations of the melt by the tundish/ladle lining refractory; and to absorb powder/aggregate which may have accumulated at the bottom of an empty tundish/ladle.
  • the known powder form metallurgical fluxes it is unacceptable, from environmental and occupational health safety viewpoints, to pour molten metal onto powder flux placed at the bottom of a ladle or tundish as this would create unacceptable amount of dust (airborn particulate could be above the allowable limit). Whereas the pelletised or granular form minimises the amount of dust generated, it is easier and safer to handle and therefore more suitable for this application.
  • another aspect of the invention involves a method of placing a metallurgical flux composite in pellet or granular form at the bottom of a tundish or ladle before pouring the ferrous melt or optionally injecting the flux into the melt.
  • Another form of the invention involves placing the metallurgical granule into the pouring stream or on top of molten metal.
  • the raw materials which may be utilised to constitute the pellets may include kaolin, flint clay, china clay, calcined flint clay, fly ash, boiler house ash, molten slag and/or silliminide, calcium oxide (burnt lime), calcium carbonate, calcium hydroxide, magnesium oxide, dolomite, olivine, fosterite, vermicullite, carbon black, coke, graphite, exfolliating graphite, calcium fluoride, barium fluoride, calcium carbide, sodium carbonate, barium oxide, alumina, aluminium and/or a similar deoxident to aluminium.
  • insulating/metallurgical pellets can be formed with no binder, relatively small amounts of binder ie. less than 15% can be added to the raw materials.
  • the binder may be any suitable type of binder such as bentonite, sodium silicate, organic binders or cellulose based binders such as carboxy methyl cellulose, cement and gypsum.
  • the ingredients of insulating pellets containing binder comprises the same ingredients as the binderless insulating pellets, however, the burnt lime (Calcium Oxide) calcium carbonate and/or Ca(OH)_ do not need to be included.
  • the binder is less than 15% wt.
  • the raw materials making up the above composition may include kaolin, flint clay china caly, calcined flint clay, fly ash, boiler house ash, silliminide, calcium oxide (burnt lime), olivine, fosterite, vermicullite, carbon black, coke, graphite, exfolliating graphite, aluminium.
  • a process similar for pelletising the composites is as follows.
  • the constituent powders are weighed according to the appropriate formulation and transferred into a screw mixer.
  • An appropriate amount of water is added in the form of a fine spray to moisten the powder, typically the moisture level is in the range of 15-35%.
  • the moistened powder is fed into the pelletising mill in a controlled manner, ie. by fixing the speed and size of a screw feeder. Additional moisture can be introduced through steam/mist jets which are located near the disc cavity of the pelletising mill.
  • the moist powder On passing through the pelletising mill, the moist powder is formed into pellets.
  • the pellets are typically cylindrical in shape, with a diameter typically in the range of 2-8mm and a typical length of 3-15mm.
  • the pellet size being dependent on the sizing holes of the mill.
  • the pellets are transported by a conveyor belt into a moving belt drying oven, where the pellets are heated to remove all the moisture.
  • the advantage of this process is that it yields pellets which exhibit good strength and are relatively free of fines.
  • the ability to produce strong pellets, without binder or with relatively small amounts of binder is achieved by selecting the appropriate amounts of constituents of the composition.
  • the composition is such that on drying a reaction occurs within the pellet between the constituent components causing bonding and thus yielding a strong pellet.
  • the insulating composites can be granulated instead of pelletised.
  • One suitable granulation process is as follows.
  • the process consists of taking a moist premixed powder and feeding this in a controlled manner, for example by means of a screw feeder at the base of a hopper onto an inclined rotating disc (or dish), where fine water sprays further wet the mix and granulation occurs.
  • the initial moisture is typically in the range 15-35 wt ⁇ -
  • the rotating disc has numerous variable which contribute to the granulation process.
  • the variables are as follows:
  • the density and size of granules produced can be varied. Once formed the granules are hardened by a drying process.
  • a second granulation process is to initially form a hard composite, dry the composite to remove moisture and harden same, and then crush to create granules of the required size. This can typically be achieved by briquetting moist composite, drying and crushing.
  • pelletising/granulating techniques such as drum granulation, concrete mixer granulation (this is used for iron ore granulation), screw extrusion, mechanical extrusion through perforated grills or spray drying could be used.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Continuous Casting (AREA)

Abstract

Composite permettant d'ajouter un fondant isolant et/ou métallurgique à un métal fondu, et particulièrement destiné à la fabrication du fer et de l'acier. Idéalement, le composite se présente sous forme de granules ou de pellets. Dans son aspect le plus général, le composite comprend un matériau à base d'aluminosilicate, un matériau contenant du calcium et/ou du magnésium, et un matériau brut charbonneux. Des matériaux supplémentaires sont ensuite ajoutés afin de conférer des caractéristiques métallurgiques et/ou isolantes améliorées au composite.
PCT/AU1994/000083 1993-02-23 1994-02-23 Composite metallurgique/d'isolation et son procede de fabrication WO1994019496A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU61773/94A AU6177394A (en) 1993-02-23 1994-02-23 Insulating/metallurgical composite and method of manufacturing same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPL746693 1993-02-23
AUPL7466 1993-02-23

Publications (1)

Publication Number Publication Date
WO1994019496A1 true WO1994019496A1 (fr) 1994-09-01

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PCT/AU1994/000083 WO1994019496A1 (fr) 1993-02-23 1994-02-23 Composite metallurgique/d'isolation et son procede de fabrication

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WO (1) WO1994019496A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0884395A1 (fr) * 1997-06-12 1998-12-16 ALMAMET GmbH Agent exempt de fluorures pour le traitement de masses d'acier en fusion dans la poche de coulée, procédé pour sa fabrication et ses applications
EP3034633A1 (fr) * 2014-12-17 2016-06-22 Refractory Intellectual Property GmbH & Co. KG Mélange, utilisation de ce mélange et procédé de conditionnement d'une scorie située sur une fonte métallique dans un récipient métallurgique lors de la métallurgie du fer et de l'acier
JP2019077922A (ja) * 2017-10-25 2019-05-23 ダイネン株式会社 精錬又は製錬添加用成型体

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1016724A (en) * 1972-09-18 1977-09-06 Smc Corporation Flux for continuous casting of steel
US4235632A (en) * 1979-04-04 1980-11-25 Mobay Chemical Corporation Particulate slagging composition for the extended optimum continuous casting of steel
US4248631A (en) * 1979-05-02 1981-02-03 Wacker-Chemie Gmbh Casting powder for the continuous casting of steel and method for producing the same
EP0034639A1 (fr) * 1980-02-21 1981-09-02 Peterlongo, Giancarlo Fondant synthétique pour laitier d'acier
JPS5757824A (en) * 1980-09-20 1982-04-07 Sakai Kagaku Kogyo Kk Covering agent for surface of molten steel
CA1122415A (fr) * 1978-08-22 1982-04-27 Giovanni Crespi Fondant synthetique pour laitier d'acier
JPS61213309A (ja) * 1985-03-19 1986-09-22 Nippon Steel Corp 溶銑脱燐スラグを原料とする精錬用フラツクスの製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1016724A (en) * 1972-09-18 1977-09-06 Smc Corporation Flux for continuous casting of steel
CA1122415A (fr) * 1978-08-22 1982-04-27 Giovanni Crespi Fondant synthetique pour laitier d'acier
US4235632A (en) * 1979-04-04 1980-11-25 Mobay Chemical Corporation Particulate slagging composition for the extended optimum continuous casting of steel
US4248631A (en) * 1979-05-02 1981-02-03 Wacker-Chemie Gmbh Casting powder for the continuous casting of steel and method for producing the same
EP0034639A1 (fr) * 1980-02-21 1981-09-02 Peterlongo, Giancarlo Fondant synthétique pour laitier d'acier
JPS5757824A (en) * 1980-09-20 1982-04-07 Sakai Kagaku Kogyo Kk Covering agent for surface of molten steel
JPS61213309A (ja) * 1985-03-19 1986-09-22 Nippon Steel Corp 溶銑脱燐スラグを原料とする精錬用フラツクスの製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DERWENT ABSTRACT, Accession No. 39997E/20, Class M24; & JP,A,57 057 824 (SAKAI KAGAKU KOGYU), 7 April 1982. *
DERWENT ABSTRACT, Accession No. 86-289365, Class M24; & JP,A,61 213 309 (HAMADA JUTO KK (YAWA)), 22 September 1986. *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0884395A1 (fr) * 1997-06-12 1998-12-16 ALMAMET GmbH Agent exempt de fluorures pour le traitement de masses d'acier en fusion dans la poche de coulée, procédé pour sa fabrication et ses applications
EP3034633A1 (fr) * 2014-12-17 2016-06-22 Refractory Intellectual Property GmbH & Co. KG Mélange, utilisation de ce mélange et procédé de conditionnement d'une scorie située sur une fonte métallique dans un récipient métallurgique lors de la métallurgie du fer et de l'acier
WO2016096178A1 (fr) * 2014-12-17 2016-06-23 Refractory Intellectual Property Gmbh & Co. Kg Mélange, utilisation de ce mélange, et procédé de conditionnement d'un scorie qui se trouve sur une fusion de métal dans un récipient métallurgique lors d'une métallurgie de fer ou d'acier
JP2019077922A (ja) * 2017-10-25 2019-05-23 ダイネン株式会社 精錬又は製錬添加用成型体

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