WO2011141036A1 - Prétraitement chimique et préchauffage de ferraille d'acier - Google Patents

Prétraitement chimique et préchauffage de ferraille d'acier Download PDF

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Publication number
WO2011141036A1
WO2011141036A1 PCT/EP2010/002868 EP2010002868W WO2011141036A1 WO 2011141036 A1 WO2011141036 A1 WO 2011141036A1 EP 2010002868 W EP2010002868 W EP 2010002868W WO 2011141036 A1 WO2011141036 A1 WO 2011141036A1
Authority
WO
WIPO (PCT)
Prior art keywords
steel scrap
solution
alkaline
scrap
steel
Prior art date
Application number
PCT/EP2010/002868
Other languages
German (de)
English (en)
Inventor
Hans-Bernd Pillkahn
Original Assignee
Progenf Ug (Haftungsbeschränkt)
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 Progenf Ug (Haftungsbeschränkt) filed Critical Progenf Ug (Haftungsbeschränkt)
Priority to EP10720547A priority Critical patent/EP2569455A1/fr
Priority to PCT/EP2010/002868 priority patent/WO2011141036A1/fr
Publication of WO2011141036A1 publication Critical patent/WO2011141036A1/fr

Links

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
    • 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
    • C21C5/527—Charging of the electric furnace
    • 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
    • C21C5/56—Manufacture of steel by other methods
    • C21C5/562—Manufacture of steel by other methods starting from scrap
    • C21C5/565—Preheating of 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • 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
    • C22B7/006—Wet processes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
    • G01D11/00—Component parts of measuring arrangements not specially adapted for a specific variable
    • G01D11/30—Supports specially adapted for an instrument; Supports specially adapted for a set of instruments
    • 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 invention relates to a method for processing steel scrap with metallic coatings and / or organic coatings for steel and cast iron production.
  • the steel and cast iron production takes place today primarily by means of blow molding processes, in particular the LD process, via cupola furnaces and via electrical steel processes.
  • the trend is towards electrical steel production with electric arc furnaces and induction shaft furnaces, which can also be driven, and in particular with 100% scrap iron.
  • electrical energy is used to melt the steel scrap used.
  • electric arc furnaces the heat is generated by arcs between one or more electrodes and the feedstock. Both AC electric arc furnaces and DC electric arc furnaces are known. Alternatively, the heat can be generated by induction as in shaft furnaces.
  • natural gas-fired furnaces for smelting steel secondary raw materials Schot-ETM
  • PEM Primary Energy Melter
  • steel or cast iron is melted from steel scrap and possibly other feedstocks such as sponge iron and alloying elements.
  • a slag layer is formed in which unwanted components are collected for the steel.
  • the slag layer closes the melt upwards and thus protects it from the atmosphere.
  • the high calorific waste gas can be used to preheat scrap.
  • the aim of scrap preheating is to increase the scrap utilization rate and to reduce CO 2 emissions through reduced use of pig iron.
  • the exhaust gases can be used to preheat the steel scrap to be melted in the crucible.
  • an afterburning of the exhaust gases is therefore necessary.
  • CO afterburning for example, a heating in the presence of oxygen to at least 600 ° C, for the destruction of other volatile organic substances heating to at least 750 ° C at a residence time of 1, 5 s necessary.
  • Dioxins and furans decompose only at temperatures above 850 ° C, wherein also a residence time of at least 1, 5 s is necessary.
  • the exhaust gas must be cooled as quickly as possible to a temperature of below 250 ° C, otherwise it would lead to a de novo Synthesis of dioxins and furans in a temperature window between about 300 and 800 ° C can come.
  • the task is to provide a method for processing steel scrap available, which allows the Schrottvor-40rmung without entailing an increased formation of dioxins and furans, which must be eliminated by a complex post-combustion.
  • the process according to the invention is particularly advantageous when the work-up concerns metal-coated steel scrap, in particular with zinc or tin or hybrid-coated steel scrap.
  • metal-coated steel scrap in particular with zinc or tin or hybrid-coated steel scrap.
  • an at least partial detachment of the applied metal layer takes place during the treatment with the alkaline / acidic solution. If necessary, this can be recycled directly from the solution, which further increases the overall cost-effectiveness of the process.
  • the method according to the invention can be used for any types of metal-coated and uncoated blades, for example both for production-fresh scraps and for old scraps.
  • the material flow should be directed before reprocessing in the sense of treatable Schratten and possibly sorted.
  • This time saving is used to effectively reduce today's performance-enhancing addition of fuels such as natural gas and / or coal and oxygen for the actual smelting process. This results in a significant potential for reducing the CO2 emission of electrical steel production even at the level of electrical steel production itself.
  • a mechanical pretreatment and processing of the scrap is carried out in order to increase the contact surfaces to the solution.
  • the mechanical pretreatment can in particular consist in a comminution of the parts, for example by shredding. Other types of roughening and deformation are also suitable.
  • the surface of the steel scrap is increased and the number of attack points for the solution, which are not yet coated with a passivation layer, increased. From the impurities created by the pretreatment, the detachment of the coatings can continue.
  • the individual scrap parts are brought to a manageable size.
  • the detachment of the organic surface coverings and, where appropriate, the metal layer from the steel scrap can be carried out both in alkaline and in acidic solution, where appropriate, a sequentially switched detachment in both media would be conceivable.
  • Detachment in acidic solution has the advantage that it can be carried out faster and at a lower temperature, however, certain amounts of iron also go into solution, which may in some cases have to be separated off during the recovery of the coating metal.
  • the presence of oils and fats in acidic solutions has a strong inhibitory action against iron dissolution.
  • the inventive partial process steps in the replacement of organic and metallic surface coatings complement each other.
  • the invention relates in particular to the workup of galvanized steel scrap.
  • the energy savings in the smelting process and the concomitant recovery of the metallic raw materials, especially the zinc, from the surface of the steel scrap are two resource efficiency technologies brought together by the invention.
  • the alkaline solution for pretreating the steel scrap is typically a solution of sodium or potassium hydroxide, with sodium hydroxide being preferred for reasons of cost.
  • the amount of sodium or potassium hydroxide is advantageously at least 15 wt .-% in order to ensure a sufficiently rapid detachment of a metal layer. It makes sense, moreover, to heat the alkaline solution to a temperature higher than room temperature, for example. Of at least 75 ° C, advantageously at least 85 ° C.
  • a relative movement of the solution to the steel scrap for example by stirring or similar measures should be brought about.
  • the detachment of the metal coating can take place as galvanic corrosion, that is, the metal coating serves as the anode at which the oxidation into ions of the metal takes place, while a second metal stable in the galvanic solution acts as the cathode at which hydrogen is evolved.
  • galvanic corrosion that is, the metal coating serves as the anode at which the oxidation into ions of the metal takes place, while a second metal stable in the galvanic solution acts as the cathode at which hydrogen is evolved.
  • These may be metals having a comparatively low hydrogen overvoltage as disclosed in US 5,302,260, for example, high surface area nickel- and cobalt-based materials, e.g. B.
  • Raney nickel, Raney cobalt, nickel molybdate, nickel sulfides, nickel cobalt thiospinels, etc., or metals with relatively high hydrogen overvoltage for example, a steel alloy as proposed by EP 0 996 774 B1.
  • Other metals that can be used are platinum, palladium, gold or silver.
  • Reason for the acceleration of the metal layer dissolution in the presence of another metal is the high overvoltage of hydrogen evolution z. As to zinc surfaces and the resulting inhibition of the process. For this reason, it makes sense to bring the metal coating to be dissolved in electrically conductive contact with materials on which the hydrogen evolution can proceed uninhibited and which are not attacked by the alkaline solution used to dissolve the metal coating.
  • Another possibility for accelerating the dissolution of a zinc coating is the addition of iron sulfide, as proposed by EP 1 626 098 A2.
  • An acceleration of the dissolution of the metal coating can also be done by applying an external voltage to the anode and the cathode. On the one hand in this way, although the energy consumption is increased, on the other hand, especially in cases where the steel scrap is in the form of bundles with hard to reach surfaces, the dissolution rate can be brought to an acceptable level.
  • EP 0 479 326 B1 A further possibility for increasing the dissolution rate is proposed by EP 0 479 326 B1, namely the addition of an oxidizing agent, in particular sodium nitrate.
  • Galvanized steel scrap may also be, prior to incorporation into the alkaline solution, at a relatively high temperature above the melting point of zinc of 419 ° C, for example at a temperature of at least 500 or 600 ° C ⁇
  • the period of time over which the steel scrap is kept at this temperature should preferably be about 10 to 15 minutes.
  • the heating causes the zinc from the zinc coating in the steel and iron diffuses out of the steel into the zinc coating, whereby the electrical contact between the metals increases at the surface, so that the galvanic corrosion resistance of the steel scrap increases.
  • the period of immersion of galvanized steel scrap in the alkaline solution is typically a maximum of two hours, for example 30 to 60 minutes, but may be shorter if additional measures are used to speed up the dissolution.
  • a sulfuric acid solution is typically used therefor, which typically contains 100 to 300 g / l, preferably 150 to 250 g / l of sulfuric acid.
  • significantly lower temperatures and a shorter time suffice, for example 20 to 60 ° C., in particular about 40 ° C.
  • a certain disadvantage of acid dezincification is that a small proportion of the iron from the steel scrap also goes into solution, at the indicated temperatures and times, however, the undesired iron entry is kept comparatively low.
  • the prior art discloses ways of removing the iron from a solution, for example precipitation in the form of the hydroxide, in the form of jarosite, goethite or hematite.
  • the corresponding methods are z. B. from Ullmann's Encyclopedia of Industrial Chemistry, 4th ed., Volume 24, p 602 et seq. Known.
  • the metal removed from the steel scrap, in particular the zinc, is recovered in a conventional manner by means of electrolysis.
  • the steel scrap before or after introduction into the alkaline or acidic solution or after separation of this solution additionally with a paint stripper in Be brought in contact.
  • Paint strippers with which organic contaminants such as paints can be removed are known in principle from the prior art.
  • alkaline paint strippers are usually organic solvents such as aliphatic or aromatic hydrocarbons, chlorinated hydrocarbons, alcohols, glycol ethers, dicarboxylic acid esters, acetone, etc. is particularly common Methylene chloride used for the removal of paints from metal surfaces.
  • paint strippers are phenols, formic acid and hydrofluoric acid esters, benzyl formate, N-methylpyrrolidone together with an alkanolamine or hydrogen peroxide.
  • the effect can be optimized by adding cosolvents, emulsifiers, evaporation retardants, wetting agents, activators and thickeners.
  • pretreatment in an alkaline solution will often be sufficient to remove varnishes, oils, etc., this may be the case in acid pretreatment. not the case.
  • the additional treatment with a paint remover thus has special importance in the pretreatment in acid, especially sulfuric acid solution. Possibly.
  • the treatment may also be combined with an alkaline solution and the treatment with an acidic solution, for example in such a way that the organic impurities are first removed from the metals with an alkaline solution, while the detachment of the metal layer takes place essentially during the subsequent acid treatment ,
  • the method according to the invention in connection with an electric furnace, in particular an electric arc furnace, z. B. so-called.
  • UHP furnaces Ultra High Power
  • it may be a shaft furnace or finger shaft furnace, wherein the shaft serves to be filled on the one hand with the steel scrap and on the other hand to pass the exhaust gases along the steel scrap in order to preheat this to an elevated temperature.
  • other furnaces which are operated for example with natural gas.
  • the exhaust gas flow usually has a temperature in a height of about 1000 ° C.
  • the steel scrap can already be preheated to a significantly elevated temperature, the z. B. between 300 and 1000 ° C, in particular at about 700 ° C. Accordingly, the time required to completely melt the steel scrap by means of arcs or induction is significantly reduced. As less time is needed for the melting process In addition, the overall process within the furnace will be faster, so that tapping may occur at shorter intervals. Overall, therefore, the efficiency of a melting furnace operated according to the invention increases not only in terms of energy, but also in terms of productivity.
  • the operating time gained can be used in electric furnace so that when used with comparable performance of the prior art today and the melting performance to achieve short Abstichintervalle increasing additives such as natural gas, oxygen and coal no longer need to be used in today's scale. This reduces carbon dioxide emissions at the smelting stage and contributes significantly to the environmental compatibility of the steel and cast iron manufacturing process.
  • the waste heat remaining after scrap preheating can be used to heat the alkaline or acidic baths used to strip the coatings.
  • the filter dusts of electric steelworks contain valuable raw materials in the form of metal oxides, in particular iron oxide, chromium oxide and nickel oxide. Zinc oxide virtually no longer occurs in the process according to the invention, since the zinc was removed in the preliminary de-zincing step. Possible reprocessing processes of the dusts are reintroduction into the metallurgical cycle, magnetic separation processes or pyrometallurgical processes.
  • the invention is explained schematically in FIG. 1 by means of a dezincification.
  • the galvanized steel scrap is brought into the Entzinkungsbad and there freed of its zinc layer.
  • the clean and descaled steel scrap is preheated in a shaft in countercurrent through the hot exhaust gases of the electric furnace, before the preheated steel scrap finally enters the actual electric furnace in which the steel production takes place.
  • the solution used in the dezincing bath to remove the zinc layer from the steel scrap is fed to zinc recycling.

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

Abstract

L'invention concerne un procédé de traitement de ferraille d'acier, selon lequel la ferraille d'acier est préchauffée à l'aide de gaz brûlés produits dans le four de fusion. Afin d'empêcher que des dioxines, des furanes ou d'autres substances organiques problématiques ne se forment dans les gaz brûlés lors du préchauffage de la ferraille d'acier, cette dernière est déjà préalablement traitée avant le préchauffage en étant introduite dans une solution alcaline et/ou acide. Les composants de la ferraille d'acier responsables de la production de dioxines et de furanes dans les gaz brûlés sont simultanément éliminés.
PCT/EP2010/002868 2010-05-10 2010-05-10 Prétraitement chimique et préchauffage de ferraille d'acier WO2011141036A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP10720547A EP2569455A1 (fr) 2010-05-10 2010-05-10 Prétraitement chimique et préchauffage de ferraille d'acier
PCT/EP2010/002868 WO2011141036A1 (fr) 2010-05-10 2010-05-10 Prétraitement chimique et préchauffage de ferraille d'acier

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2010/002868 WO2011141036A1 (fr) 2010-05-10 2010-05-10 Prétraitement chimique et préchauffage de ferraille d'acier

Publications (1)

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WO2011141036A1 true WO2011141036A1 (fr) 2011-11-17

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111910044A (zh) * 2020-09-10 2020-11-10 山东众亿赫贸易有限公司 一种轻型废钢的预处理方法及其使用的装置

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3905882A (en) * 1974-09-25 1975-09-16 Harold G Hudson Electrolytic zinc salvaging method
DE2709515A1 (de) * 1976-03-04 1977-09-15 British Steel Corp Verfahren und vorrichtung zur entfernung von ueberzuegen auf metallischen gegenstaenden
BE892897A (fr) * 1982-04-19 1982-10-19 Ct D Etude Et De Documentation Procede et appareil de recuperation des composants d'objets en acier galvanise.
EP0479326A1 (fr) * 1990-10-05 1992-04-08 AK Steel Corporation Enlèvement du zinc de riblons d'acier galvanisé par une solution alcaline
JPH05125459A (ja) * 1991-10-30 1993-05-21 Nippon Steel Corp 亜鉛めつき鋼板屑の脱亜鉛方法
EP0772015A1 (fr) * 1995-03-31 1997-05-07 Nippon Steel Corporation Procede et dispositif de prechauffage et de fusion de ferraille
US6258248B1 (en) * 1996-07-17 2001-07-10 Metals Investment Trust Limited Process for dezincing galvanized steel using an electrically isolated conveyor
JP2002121612A (ja) * 2000-10-19 2002-04-26 Nkk Corp 冷鉄源の溶解方法
DE102008056812A1 (de) * 2008-11-11 2010-05-27 Drt Deutsche Rohstofftechnik Gmbh Schrottvorwärmung

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3905882A (en) * 1974-09-25 1975-09-16 Harold G Hudson Electrolytic zinc salvaging method
DE2709515A1 (de) * 1976-03-04 1977-09-15 British Steel Corp Verfahren und vorrichtung zur entfernung von ueberzuegen auf metallischen gegenstaenden
BE892897A (fr) * 1982-04-19 1982-10-19 Ct D Etude Et De Documentation Procede et appareil de recuperation des composants d'objets en acier galvanise.
EP0479326A1 (fr) * 1990-10-05 1992-04-08 AK Steel Corporation Enlèvement du zinc de riblons d'acier galvanisé par une solution alcaline
JPH05125459A (ja) * 1991-10-30 1993-05-21 Nippon Steel Corp 亜鉛めつき鋼板屑の脱亜鉛方法
EP0772015A1 (fr) * 1995-03-31 1997-05-07 Nippon Steel Corporation Procede et dispositif de prechauffage et de fusion de ferraille
US6258248B1 (en) * 1996-07-17 2001-07-10 Metals Investment Trust Limited Process for dezincing galvanized steel using an electrically isolated conveyor
JP2002121612A (ja) * 2000-10-19 2002-04-26 Nkk Corp 冷鉄源の溶解方法
DE102008056812A1 (de) * 2008-11-11 2010-05-27 Drt Deutsche Rohstofftechnik Gmbh Schrottvorwärmung

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111910044A (zh) * 2020-09-10 2020-11-10 山东众亿赫贸易有限公司 一种轻型废钢的预处理方法及其使用的装置

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