EP0877830A1 - Procede pour separer de l'etain et si besoin du cuivre d'un bain de ferrailles en fusion, notamment d'un bain de fer blanc ou d'un bain metallique en fusion - Google Patents

Procede pour separer de l'etain et si besoin du cuivre d'un bain de ferrailles en fusion, notamment d'un bain de fer blanc ou d'un bain metallique en fusion

Info

Publication number
EP0877830A1
EP0877830A1 EP97938671A EP97938671A EP0877830A1 EP 0877830 A1 EP0877830 A1 EP 0877830A1 EP 97938671 A EP97938671 A EP 97938671A EP 97938671 A EP97938671 A EP 97938671A EP 0877830 A1 EP0877830 A1 EP 0877830A1
Authority
EP
European Patent Office
Prior art keywords
iron
carbon
phase
bath
sulfur
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP97938671A
Other languages
German (de)
English (en)
Inventor
Alfred Edlinger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Holcim Ltd
Original Assignee
Holderbank Financiere Glarus AG
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 Holderbank Financiere Glarus AG filed Critical Holderbank Financiere Glarus AG
Publication of EP0877830A1 publication Critical patent/EP0877830A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • 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
    • C22B25/00—Obtaining tin
    • C22B25/06—Obtaining tin from scrap, especially tin scrap
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • 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 invention relates to a method for separating tin and, if necessary, copper from scrap melts, in particular tinplate melts or metallic melts, such as are formed in the course of the processing of waste or combustion residues containing metal oxide
  • a method for processing waste or metal oxide-containing metal combustion residues has already been disclosed in EP 707 083, in which a reduction was subsequently carried out after at least partial oxidation of the melt to slag with the separation of a metal bath.
  • a reduction was subsequently carried out after at least partial oxidation of the melt to slag with the separation of a metal bath.
  • copper is brought into the iron bath, with non-ferrous metals in the Can seep out in the form of raw bronze.
  • crude bronze had leached out at a temperature of approx. 1500 ° C.
  • a raw copper with an iron content of approximately 4% by weight was generally formed, although relatively high copper contents still remain in the iron bath.
  • the remaining iron alloy typically contains about 8% by weight copper.
  • WO 96/24696 has disclosed a process for producing pig iron or steel and cement clinker from slag, in which a ferrite slag is formed and is likewise reduced in a reduction reactor with the formation of an iron bath and in the sintering phase with the combustion of carbon .
  • the pig iron bath can subsequently be refreshed, whereby copper contents can remain in the steel, which are too high for a number of other uses.
  • Iron baths used specifically for refining slags, and in particular pig iron baths contain more or less high copper contents, depending on the history of the slags.
  • the tin content of steel is usually between 0.015 and 0.02% by weight in the steel. Extrapolation for scrap results in tin contents of 0.1% by weight and the presence of tin in such large amounts leads to a product which can only be used to a limited extent after the scrap melt. This applies all the more when tinplate melts are produced and it is therefore a simple and reliable method for separating tin of essential economic importance in order to arrive at economically usable melt products.
  • Scrap melting processes, and in particular tinplate melting, have so far generally resulted in a product with limited use, which is not suitable for a number of applications is more appropriate.
  • a tin content of more than 500 ppm leads to significantly reduced strength and deformation properties of the product, so that a simple and safe method for separating tin can significantly improve the value of the melt product.
  • the invention now aims to reduce the tin content and, if necessary, the copper content of metallic melts or of scrap melts in a particularly simple manner, whereby to solve this problem it is proposed that the C content of the melt be 3 to 4.2% by weight. % is set and that hot wind, oxygen or oxygen-enriched air is locally blown onto partial areas of the surface of the melt pool, SnO being discharged from the zone formed between the carbon-rich bath and the iron oxides formed by inflation using a redox gradient via the gas phase.
  • a reduction potential is set, as is typical for pig iron. Due to the fact that hot wind or oxygen is locally blown onto partial areas of the surface of the molten bath, a redox gradient is formed between a locally formed iron oxide phase and the iron carbon of the bath, which enables the selective oxidation of tin to divalent tin and in this way due to The high vapor pressure of SnO causes SnO to constantly evaporate from the equilibrium in the phase of the redox gradient between the iron oxide phase and the iron carbon.
  • Iron oxide is thus continuously separated off, the areas over which such separation of tin oxide succeeds in the divalent stage being limited to a spherical cap surrounding the iron oxide phase with a pronounced redox gradient.
  • the correspondingly high carbon content of the melt is necessary, with this zone between iron oxide phase and iron carbon in addition to SnO Arsenic as a trivalent oxide (AS2O3) can also be removed via the gas phase.
  • a complete separation of tin is usually possible with blowing times of less than 20 minutes, with the advantage that it can be removed together with volatile SnO A s-III oxides.
  • the procedure according to the invention is advantageously such that the C content of the bath during the local inflation of oxygen to 3 to 4.2% by weight by blowing in carbon or is held by carbon carriers.
  • the oxygen or air lance is directed towards a focal spot, which ensures the formation of the transition zone with the redox gradient to the surrounding iron carbon.
  • the setting and maintenance of the corresponding carbon content ensures the corresponding redox gradient over the entire blowing time and thus the reliable separation of evaporating SnO from the transition zone, the metallic tin being able to be oxidized selectively and quantitatively to SnO.
  • the process according to the invention is advantageously carried out in such a way that oxygen is introduced via an inflation lance and carbon is introduced through the bottom nozzles of a converter, the procedure advantageously being that the zone with the redox gradient is maintained until the tin content has dropped below 500 ppm becomes.
  • the high carbon content leads to the formation of the two phases, which enables a substantial depletion of copper if necessary.
  • Further equally undesirable copper can subsequently advantageously be removed in such a way that, after tin has been separated off, Cu is separated off by introducing sulfur into the molten metal.
  • the melting temperature is in particular in the case of tinplate melts and a carbon content of approximately 4.2% by weight at approximately 1350 ° C.
  • iron II and iron in particular become III-oxides are formed, which subsequently form the required zone with a redox gradient with the carbon content of the iron in the vicinity of the firing spot of the lances, which in turn ensures the safe oxidation of metallic tin to SnO and thus the separation via the Ensure gas phase.
  • the process is of course economically viable if cheap coal qualities, such as, for example, high-sulfur pet coke, a carbon-containing residue from petroleum distillation with about 7% by weight sulfur are used for melting, and in particular for melting, scrap becomes.
  • the resulting high sulfur input can be used directly to reduce the copper content.
  • the procedure is advantageously that of melting with sulfur-containing carbon carriers copper stone formed at temperatures above 1400 ° C, in particular about 1500 ° C, is withdrawn from the iron bath.
  • the procedure is advantageously such that sulfur is introduced or applied in at least a stoichiometric amount based on Cu, whereupon the liquid Cu2 ⁇ - (copper stone) phase formed is drawn off.
  • the process according to the invention is therefore advantageously carried out in such a way that the iron-rich melts are saturated with carbon or are used as a pig iron bath, whereupon in a first process step a phase separation into an iron-rich phase containing Cu in amounts of 0.5 to 2% by weight and a phase Cu-rich phase containing residual iron less than 10% by weight takes place, whereupon the iron-rich phase is mixed with sulfur and the floating Cu2S phase is drawn off.
  • the sulfur can be introduced in a particularly simple manner in the form of sulfur vapor.
  • the process according to the invention is advantageously carried out in such a way that S in the form of S- Steam is introduced in a stoichiometric amount based on Cu, preferably S-steam is used in an amount exceeding the stoichiometric amount based on Cu by a factor of 1.5 to 2.5.
  • the desulfurization of the iron or steel bath after tapping the copper sulfide phase can be carried out in a simple manner so that CaC2 and / or MgO is used to desulfurize the metal bath.
  • clinker, pozzolana slag or a waste incineration slag with a basicity (CaO / SiO 2) between 1.3 and 1.7 is advantageously used for desulfurization, such a procedure having the advantage that the clinker or the pozzolana slag Integrates sulfur from the pig iron bath into the clinker structure practically quantitatively.
  • Such a procedure is advantageous in terms of cement technology, since it can reduce the amount of gypsum added during cement production.
  • the sulfur can be introduced in a particularly simple manner via under-bath nozzles.
  • a temperature level of around 1500 ° C is sufficient at the beginning for the desulfurization of pig iron.
  • Carbon reduces the solubility of liquid copper in molten pig iron, which means that a two-phase melt can be formed with a correspondingly high carbon content.
  • an iron-rich phase with approximately 1% by weight of copper and a copper-rich phase with approximately 6% by weight of iron can be formed, the two phases being easily separated from one another by decanting at approximately 1500 ° C.
  • Pig iron fractions as can be used in the course of the present invention, typically contain Cu contents between 0.1 and 8% by weight.
  • the copper-rich fraction withdrawn can be given to a primary copper smelter with a contribution margin.
  • the iron-rich fraction can then be decoupled by sulfur, whereby iron-containing copper sulfide can be floated onto the pig iron bath and drawn off. In principle, this copper sulfide can also be sold to a primary smelter with a low contribution margin.
  • the pig iron left behind generally has a relatively high sulfur content of the order of a few percent by weight.
  • a typical sulfur content here is around 2% by weight.
  • Desulphurization is achieved in a conventional manner under basic and reducing conditions, for example with calcium carbide or magnesium, after which the steel can then be refined. If clinker or pozzolana slags are used for the desulfurization of the pig iron bath, sulfur contents of less than 60 ppm can be easily achieved in the pig iron.
  • Devices such as rinsed pans and RH or DH processes can be used for the sulfurization process in secondary metallurgy.
  • Sulfur vapor can be introduced in a simple manner via under-bath nozzles.
  • clinker phases or liquid pozzolana slags or a waste incineration slag with a basicity (CaO / Si ⁇ 2) between 1.3 and 1.7 in addition to desulfurization of the pig iron bath, an improvement in the cement technology properties is achieved at the same time, since the sulfur binding in the clinker, as mentioned above, has a number of advantages.
  • copper stone Because of the sulfur introduced via pet coke, a so-called “copper stone” was formed, in which nickel and iron were dissolved in addition to copper.
  • the copper stone is a thin, complex sulfide composed of Fe, Cu, Ni and traces of other metals ("sulfide pictures"). The metals Zn, Pb and some phosphorus go into the gas phase.
  • the copper stone was removed from the iron bath at approx. 1500 ° C.
  • the pig iron left behind still had a Cu content of approx. 500 ppm.
  • the slag was desulphurized to approx. 1000 ppm S in an iron bath using a slag obtained from waste incineration (CaO / Si ⁇ 2 between 1.3 and 1.7).
  • the desulfurized iron bath was "tinned" by means of a hot wind jet (1100 ° C). About 30 to 90 - ⁇ hot air was required per ton of pig iron. The de-tinning process was completed in 10-20 minutes. The final tin content of the pig iron thus obtained was less than 200 ppm.
  • the crude iron melt had a bath temperature of 1450 to 1550 ° C, the final carbon content being about 1.5%.
  • Hot air was used to freshen up to a carbon content of 0.5%.
  • the "final freshening" was done with technically pure oxygen in the LD or OBM process in order to obtain the lowest possible final nitrogen contents in the crude steel.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé pour séparer de l'étain et si besoin du cuivre d'une masse de ferrailles en fusion, notamment une masse de fer-blanc ou une masse métallique en fusion, telles qu'elles sont utilisées dans le retraitement des déchets ou de résidus de combustion contenant de l'oxyde métallique. On règle la teneur en carbone de la masse en fusion à une valeur comprise entre 3 à 4,2 % en poids et on procède au soufflage local d'air chaud, d'oxygène ou d'air enrichi en oxygène sur des zones partielles de la surface de la masse en fusion. Le SnO est extrait à partir de la zone formée entre le bain enrichi en carbone et les oxydes de fer formés par soufflage, avec un gradient rédox par la phase gazeuse.
EP97938671A 1996-09-10 1997-09-09 Procede pour separer de l'etain et si besoin du cuivre d'un bain de ferrailles en fusion, notamment d'un bain de fer blanc ou d'un bain metallique en fusion Withdrawn EP0877830A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
AT529/96U 1996-09-10
AT52996 1996-09-10
AT385/97U 1997-06-23
AT38597 1997-06-23
PCT/AT1997/000196 WO1998011263A1 (fr) 1996-09-10 1997-09-09 Procede pour separer de l'etain et si besoin du cuivre d'un bain de ferrailles en fusion, notamment d'un bain de fer blanc ou d'un bain metallique en fusion

Publications (1)

Publication Number Publication Date
EP0877830A1 true EP0877830A1 (fr) 1998-11-18

Family

ID=25592540

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97938671A Withdrawn EP0877830A1 (fr) 1996-09-10 1997-09-09 Procede pour separer de l'etain et si besoin du cuivre d'un bain de ferrailles en fusion, notamment d'un bain de fer blanc ou d'un bain metallique en fusion

Country Status (4)

Country Link
US (1) US6106587A (fr)
EP (1) EP0877830A1 (fr)
AU (1) AU4104297A (fr)
WO (1) WO1998011263A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6478847B1 (en) 2001-08-31 2002-11-12 Mueller Industries, Inc. Copper scrap processing system
CN102102154A (zh) * 2010-12-22 2011-06-22 中南大学 一种锡的低温熔盐清洁冶金方法
CN107267782B (zh) * 2017-05-05 2019-02-01 中南大学 一种从高锡钨精矿中综合回收锡钨的方法
CN112575194B (zh) * 2020-11-25 2021-12-17 中南大学 一种用于强化废旧焊锡中锡氧化挥发的添加剂及其应用

Family Cites Families (13)

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Publication number Priority date Publication date Assignee Title
GB1192510A (en) * 1968-11-12 1970-05-20 Meherwan Cavasji Irani Removal of Copper from Molten Iron and Steel
GB2021155A (en) * 1978-05-16 1979-11-28 British Steel Corp Removing Tin From Cast Iron
GB2039859B (en) * 1979-01-16 1982-12-08 Ryazan Z Proizv I Obrabot Tsve Recovery of tin from stanniferous material
AU8895482A (en) * 1981-10-09 1983-04-14 Unisearch Limited Submerged arc furnace smelting and fuming of tin concentrates
SU1148872A1 (ru) * 1983-04-11 1985-04-07 Магнитогорский горно-металлургический институт им.Г.И.Носова Способ удалени меди из расплава чугуна и стали
JPH06299266A (ja) * 1993-04-12 1994-10-25 Nippon Steel Corp 錫を含む鉄鋼スクラップから錫を分離回収する方法
JPH07179923A (ja) * 1993-12-22 1995-07-18 Nippon Steel Corp 金属の溶解・精錬法
AT403294B (de) * 1994-10-10 1997-12-29 Holderbank Financ Glarus Verfahren zum aufarbeiten von müll oder von metalloxidhaltigen müllverbrennungsrückständen sowie vorrichtung zur durchführung dieses verfahrens
CH688325A5 (de) * 1994-11-25 1997-07-31 Holderbank Financ Glarus Verfahren zur Aufbereitung von festen Rueckstaenden aus Muellverbrennungsanlagen und Vorrichtung zur Drchfuehrung des Verfahrens.
AT403290B (de) * 1995-02-07 1997-12-29 Holderbank Financ Glarus Verfahren zur herstellung von roheisen oder stahl und zementklinker aus schlacken
US5588982A (en) * 1995-05-01 1996-12-31 Alabama Power Company Process for producing foudry iron
WO1997012065A1 (fr) * 1995-09-27 1997-04-03 Sumitomo Metal Industries, Ltd. Procede de fusion de ferrailles contenant de l'etain
AT405944B (de) * 1996-04-19 1999-12-27 Holderbank Financ Glarus Verfahren zum reduzieren von oxidischen schlacken

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9811263A1 *

Also Published As

Publication number Publication date
WO1998011263A1 (fr) 1998-03-19
AU4104297A (en) 1998-04-02
MX9803409A (es) 1998-11-29
US6106587A (en) 2000-08-22

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