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WO1996031630A1 - Reutilisation de fines metallurgiques - Google Patents

Reutilisation de fines metallurgiques Download PDF

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Publication number
WO1996031630A1
WO1996031630A1 PCT/GB1996/000821 GB9600821W WO9631630A1 WO 1996031630 A1 WO1996031630 A1 WO 1996031630A1 GB 9600821 W GB9600821 W GB 9600821W WO 9631630 A1 WO9631630 A1 WO 9631630A1
Authority
WO
WIPO (PCT)
Prior art keywords
slurry
fines
agglomerates
carbon
dust
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.)
Ceased
Application number
PCT/GB1996/000821
Other languages
English (en)
Inventor
Dirk Osing
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.)
Heckett Multiserv PLC
Original Assignee
Heckett Multiserv PLC
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
Priority claimed from DE1995112560 external-priority patent/DE19512560A1/de
Priority claimed from DE19537283A external-priority patent/DE19537283A1/de
Application filed by Heckett Multiserv PLC filed Critical Heckett Multiserv PLC
Priority to BR9604790A priority Critical patent/BR9604790A/pt
Priority to AU51599/96A priority patent/AU719637B2/en
Priority to EP19960908291 priority patent/EP0820531A1/fr
Priority to JP53009696A priority patent/JPH11503201A/ja
Priority to KR1019970707005A priority patent/KR19980703606A/ko
Publication of WO1996031630A1 publication Critical patent/WO1996031630A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/242—Binding; Briquetting ; Granulating with binders
    • C22B1/244—Binding; Briquetting ; Granulating with binders organic
    • C22B1/245—Binding; Briquetting ; Granulating with binders organic with carbonaceous material for the production of coked agglomerates
    • 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
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/242—Binding; Briquetting ; Granulating with binders
    • C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
    • 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
    • C22B7/02—Working-up flue dust
    • 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 of use of a wide range of metal containing materials which are otherwise used with difficulty or just dumped as waste.
  • One suitable material is iron ore fine dust. This is difficult to dispose of.
  • pelletising fine ores having a grain diameter of under about 0.2 mm are wetted and mixed with binders, e.g. bentonite, to form lumps.
  • binders e.g. bentonite
  • the pellets are subjected to flame hardening or sintering because this is the only way in which such fines can only be used
  • gases contain H? and CO and also C0 2 , H 2 O, CH ⁇ and N 2 .
  • Preparation takes place in a series of fluidised bed reactors, connected in series, in which the degree of reduction increases from reactor to reactor to reach values of metallisation of between 92 and 94% at the exit of the last fluidised bed reactor.
  • the fines reduced in this manner are then hot briquetted in order to obtain the lump form which is necessary for the subsequent metallurgical process.
  • ferrous dusts accumulate, which are very fine and extremely reactive.
  • the dusts also contain proportions of non-converted carbon. Such fines cannot be blown or injected into a metallurgical furnace because they have too high a density.
  • high quality steel is meant a grade of steel which is intended generally for heat treatment such as hardening and tempering.
  • High quality steel has a higher purity than quality or basic steel (cf. Brockhaus. Naturwissenschaften undtechnik (Natural Science and Technology), special edition 1989. volume 1 , key word).
  • Such steels are produced in electric arc furnaces from steel scrap and alloying constituents.
  • the dust contained in the smelting gases is very finely divided and has a high specific weight more than 4 grams per cubic centimetre. The dust is separated in the electric filters installed beyond the electric furnace.
  • metal such as screws, and cleaning rags, cigarette ends and working gloves, yoghurt cartons and plastic bags can also be dumped by untidy workmen in the rolling mill scale
  • All metal dusts and slurries arising during the production of basic, quality and high quality steel are finely divided (fine granulometry in the grain size range of a few microns up to 1 mm) and contain alloying metals.
  • These alloying metals include chiefly chromium, cobalt, nickel, lead, manganese, tungsten, titanium, vanadium, zinc and molybdenum, which are added to the individual grades of steel in differing amounts according to pre-set recipes and together with the iron, are responsible for the heaviness of the dusts and slurries.
  • these dusts and slurries contain valuable substances it has not been possible to reclaim and re-use these substances to a satisfactory extent because of their inherent fineness and heaviness. In many cases the dusts containing valuable substances are dumped but this is bad for environmental protection and wasteful.
  • a method of treating a waste material containing heavy metals comprising mixing the waste material and a relatively less dense particulate material containing metal oxide material and water so as to cause an exothermic reaction and thereby form relatively dry agglomerates; sieving the agglomerates to isolate those having a size in the range of from about Omm to about 6mm; and pneumatically injecting the isolated agglomerates into a metallurgical vessel containing molten metal and under a reducing atmosphere.
  • the oxide material may be burnt lime or directly reduced iron. Most preferably the agglomerates are injected with carbon (which is required for other purposes in the metallurgical vessel such as a reduction reaction).
  • the carbon may be provided from a variety of sources and may already be in the waste material.
  • a carbon-bearing carrier material may be used. Suitable materials are coke consisting of coal or hgnite or brown coal, or petroleum coke because these cokes, owing to their surface structure and porosity, are particularly suitable to carry the fines on to their surface. However, finely divided or dust form fractions of coal or hgnite are also suitable as carrier material, just as are finely divided lightweight fractions from the shredding of plastics. The latter have a
  • carbon-containing carrier materials having volatile constituents are best.
  • the amount of volatiles in the total carbon content of the carrier materials should be greater than 8%. Lignites as well as other low coahfied types of coal, wood chippings, plastics chips, or the like can also be used.
  • the product For the promotion of the foaming of the slag, the product should have a carbon content between 20 and 40 percent by weight.
  • the carrier materials may be selected and determined by means of pre-analysis.
  • the mixed, reaction and combined products still exhibit amounts of Fe, FeO, Fe 2 O 3 , CaO and CaCOj, and the residual humidity is between 5 and 15 percent by weight.
  • the invention also makes use of the reactivity of the fines.
  • the fines react with water to form iron oxide, releasing heat.
  • the heat released during the exothermic reaction causes part of the moisture to evaporate and allows the agglomerates to become crumbly.
  • the agglomerates must have a density of about 1 ,2 to about 4 grams per cubic centimetre.
  • the delivery cross-sections of standard injection devices in the order of between '/_ (about 12mm) and 2 inches (about 50mm) made it necessary to sieve the products to grain sizes of below about 6 mm in diameter.
  • Standard injection pressures are about 4 to 5 bars for electric arc furnaces and about 5 to 6 bars for blast furnaces.
  • fines and carrier material are first mixed together and then if applicable with water or with a moist carbon-containing slurry; or carbon-containing slurry and carrier material are mixed together first and then mixed with the fines. It is possible to mix fines, carrier material and carbon- containing slurry at the same time.
  • the crumbly agglomerate is readily storable. As soon as it has reacted, it becomes inert and is suitable for pneumatic conveying. It is possible to inject product into the blast furnace, electric arc furnace, converter or cupola-type furnace and even into rotary cement kilns, (although in this respect it is no longer a metallurgical process in
  • coal slurry has only a low calorific value (because it exhibits a high proportion of sterile mine waste material which only increases the amount of slag of the metallurgical process, but contributes nothing to the foaming of the slag).
  • Preferably energy-rich slurries are used, such as result, from oil-containing rolling mill scale slurry.
  • Fuller's earth or slurries which contain hgnite dust or coke dust from coal or hgnite or waste material slurries from petrochemistry.
  • Such slurries at the same time reduce the energy required in the subsequent metallurgical process, because they provide part of the carbon requirement.
  • rolling mill scale slurry in particular is regularly interspersed with foreign bodies, as is well known, such impurities play no role in the present invention, because the foreign bodies separate from the slurries during treatment of the fines and after the thorough mixing of the components are removed by sieving. This applies also to the lumps or aggregates which may occasionally arise during mixing.
  • dusts from dry dust-extraction are suitable for admixing to the fines insofar as they do not already themselves form these fines.
  • slurries which result from the wet dust-extraction of blast furnaces, cupola-type furnaces, electric arc furnaces, converters, sintering plants and surface treatment plants for the grinding/and poUshing of metals are also suitable.
  • the corresponding dust from dry dust-extraction may be admixed to the fines insofar as they do not already themselves form these fines.
  • the additive may include sufficient lime for the lime requirement of the furnace by the addition of substances which exhibit free quicklime, CaO. So according to the invention the amount of slurry necessary to form the reaction product is increased beyond the actual requirement and fly ash is added to the reaction product in addition.
  • the free quicklime of the fly ash reacts with the residual moisture of the slurry to form calcium hydroxide Ca(OH) 2 , by which heat is also liberated.
  • the limestone favours the subsequent metallurgical process and the liberated heat makes the combined product crumbly.
  • fly ash from the flue gas in the electric filter behind the power station boiler when burning low sulphur fossil fuels includes primarily hgnite from the Rhine.
  • fly ash which accumulates during the treatment of fuels according to the dry additive process is also suitable if limestone has been added to the fuel to bind the sulphur before combustion.
  • DAP ashes are usable.
  • preparation of heavy, metal-containing slurries also includes, besides those already mentioned, grinding slurries for use in the first step of the method.
  • grinding slurries for use in the first step of the method.
  • the usually impenetrable slurries are dried at first and thereby made easy to handle.
  • the amount of quicklime in the fly ash or slag from the ladle furnace assists drying since the free quicklime reacts exothermally with the moisture of the slurry and a considerable part of the moisture inherent in the slurry evaporates thereby; the lime addition which is advantageous for the subsequent metallurgical process remains unaffected.
  • Another waste material useful in the present invention is made up of different forms of aluminium.
  • aluminium is known to be useful in deoxidation and in the
  • the sieved off fine fraction comprising carbon- containing dusts and lime-stone-containing agglomerates is mixed thoroughly with these. This final step contributes substantially lowering the density until they become blowable or injectable under air or other gas pressure.
  • the use of hgnite coke dust, petroleum coke or anthracite or dusts from slightly or low volatile coal or mixtures thereof is preferred, wherein their respective grain size is below 1 mm in diameter.
  • the addition of carbon is known to promote the foaming of slag in the subsequent metallurgical process.
  • the waste material has an organic fraction, e.g. an oil.
  • organic fraction e.g. an oil.
  • metal-containing slurries from surface machining such as. e.g. grinding slurries, or in the case of rolling mill scale slurries
  • less carbon dust will be required than for slurries which do not bring with them per se this kind of organic admixtures, e.g.
  • the colour of these spheres is beige, they have a smooth surface and exhibit a high compressive strength. Normally they are disposed of on the dump.
  • the spheres are suitable preferably as carrier for the mix consisting of heavy metal particles, lime and carbon. Bonding to the carrier is ensured by electrostatic forces as well as the moisture from the water preparation. Their content of silicon, lime and iron are helpful for the subsequent metallurgical process.
  • the invention provides; a pneumatically injectable feed material for use as an additive to the molten metal in an electric arc furnace, the material comprising the reaction product of a waste paniculate material containing heavy metal elements and oily mill scale, the material being in the form of agglomerates having a particle size from about 0mm to about 6mm;
  • a pneumatically injectable feed material for use as an additive to the molten metal in an electric arc furnace, the material comprising the reaction product of a waste paniculate material containing heavy metal elements and directly reduced iron fines, the feed material being in the form of agglomerates having a particle size from about 0mm to about 6mm;
  • Figure 2 is graphs showing exothermic reactions.
  • a high quality steel slab 2 is rolled into a sheet 3 at a rolling mill.
  • Water 5 under pressure is added to the rolling process via a nozzle 4.
  • the rolling mill scale 6 is collected as rolling mill scale slurry 7 in a trough 8 underneath the rolling mill stand 1.
  • Separately coal 10 is burned in a power station boiler 9.
  • the hot flue gas 1 1 arising is passed over heat exchanger surfaces 12 in which boiler feed water 13 circulates and which is converted into steam 14 on the heat exchanger surface 12.
  • the flue gas 11 leaves the boiler via an electric filter 33, where the finely divided fly ash 15 which is carried along and separated from the flue gas before it can be discharged through the chimney 16 into the atmosphere.
  • the rolling mill scale slurry 7 and separated fly ash 15 are fed to a first mixer 17. wherein the rolling mill scale slurry 7 and the fly ash 15 are intimately mixed. During mixing with the fly ash 15 the moist rolling mill scale slurry 7 dries out to form an agglomerate product having a crumbly consistency. The reaction is exothermic and the water evaporates.
  • the first mix 1 leaving the mixer 17 has a temperature above ambient and passed through a sieve 19. where a fine fraction 20 is sieved off.
  • the oversize 21 from the sieve 19 contains the foreign bodies and impurities present previously in the rolling mill scale slurry 7: these are discarded.
  • the fine fraction 20 having a grain size range of under 1 mm flows to a second mixer 22, where it is mixed with hgnite coke dust 23 and h ⁇ e-containing spherical agglomerates whose average grain size is between 0.5 and 2 mm.
  • the spheres 24 have been derived from a filter 25, where the boiler feed water 13 of the power station boiler 9 is prepared for passage to the turbines. After the water vapour 14 has been stress relieved in the steam turbine 34. it flows through a condenser 26, where it condenses again to form boiler feed water 13. The condensed boiler feed water 13 is forced by feed water pump through a filter 25. Quartz grains 28 are added to the filter 25, where the lime contained in the boiler feed water 13 and the iron accumulate, in order to form the spheres 24. Losses of boiler feed water 13 are compensated for by fresh water introduced via the pipe 29.
  • Results are also shown in the graph. The temperature rises slowly by a further 3.5°C in the course of 18 minutes and remains constant thereafter.

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

Abstract

Des matériaux de déchet contenant des métaux lourds sont mélangés avec des pailles huileuses ou avec des fines de minerai de fer réduit et avec un matériau porteur finement granulé ayant une densité basse jusqu'à l'obtention d'un produit de mélange émietté, dont une portion fine comprenant des grains dont la taille est comprise entre 0 et 6 mm est tamisable afin d'être injectée dans un four métallurgique. De l'eau peut être ajoutée au produit mélangé à l'aide de boues mouillées contenant du carbone. Des poussières contenant de la chaux peuvent être ajoutées.
PCT/GB1996/000821 1995-04-04 1996-04-03 Reutilisation de fines metallurgiques Ceased WO1996031630A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BR9604790A BR9604790A (pt) 1995-04-04 1996-04-03 Reutilização de finos metalúrgicos
AU51599/96A AU719637B2 (en) 1995-04-04 1996-04-03 Reuse of metallurgical fines
EP19960908291 EP0820531A1 (fr) 1995-04-04 1996-04-03 Reutilisation de fines metallurgiques
JP53009696A JPH11503201A (ja) 1995-04-04 1996-04-03 金属微粉の再利用
KR1019970707005A KR19980703606A (ko) 1995-04-04 1996-04-03 중금속함유 폐기물 처리방법 및 야금공정용 미분 제조방법 및공기로 주입가능한 공급재

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE1995112560 DE19512560A1 (de) 1995-04-04 1995-04-04 Verfahren zum Aufbereiten von metallhaltigen Stäuben oder Schlämmen zum Einblasen in einen metallurgischen Prozeß
DE19512560.0 1995-04-04
DE19526687.0 1995-07-21
DE1995126687 DE19526687A1 (de) 1995-04-04 1995-07-21 Verfahren zum Aufbereiten von metallhaltigen Stäuben oder Schlämmen zum Einblasen in einen metallurgischen Prozeß
DE19537283.0 1995-10-06
DE19537283A DE19537283A1 (de) 1995-10-06 1995-10-06 Verfahren zum Aufbereiten der Fines von reduziertem Eisenerz

Publications (1)

Publication Number Publication Date
WO1996031630A1 true WO1996031630A1 (fr) 1996-10-10

Family

ID=27215015

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1996/000821 Ceased WO1996031630A1 (fr) 1995-04-04 1996-04-03 Reutilisation de fines metallurgiques

Country Status (6)

Country Link
EP (1) EP0820531A1 (fr)
JP (1) JPH11503201A (fr)
AU (1) AU719637B2 (fr)
BR (1) BR9604790A (fr)
CA (1) CA2215409A1 (fr)
WO (1) WO1996031630A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2324081A (en) * 1997-04-07 1998-10-14 Heckett Multiserv Plc Additives for Electric Arc Furnace
WO1999028414A3 (fr) * 1997-12-02 1999-09-02 Code Gmbh Procede de refroidissement d'un melange issu d'une reaction exothermique a partir de dechets
GB2337257A (en) * 1998-05-11 1999-11-17 Heckett Multiserv Plc Treating aqueous sludge waste; additives for furnaces

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008163412A (ja) * 2006-12-28 2008-07-17 Jtekt Corp 鉄系粉末材料及びその製法、並びに製鋼原料用ブリケット

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5245518A (en) * 1975-10-08 1977-04-11 Chikara Hidaka Production process of pellets using iron ore dust generated from raw m aterial for iron manufacture as raw material
US4119455A (en) * 1977-09-28 1978-10-10 Carad, Inc. Method of recovering iron-bearing by-product flue dust
DE3727576C1 (en) * 1987-08-19 1988-09-15 Heinz Staschel Process for reprocessing fine-grained ferrous by-products from steelworks and metallurgical works to form lumpy material for use in blast furnaces
EP0499779A1 (fr) * 1991-01-24 1992-08-26 Rheinbraun Aktiengesellschaft Procédé de traitement des déchets
DE4324343A1 (de) * 1993-07-20 1995-01-26 Koeppern & Co Kg Maschf Verfahren zum Herstellen von Briketts aus Hüttenreststoffen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5245518A (en) * 1975-10-08 1977-04-11 Chikara Hidaka Production process of pellets using iron ore dust generated from raw m aterial for iron manufacture as raw material
US4119455A (en) * 1977-09-28 1978-10-10 Carad, Inc. Method of recovering iron-bearing by-product flue dust
DE3727576C1 (en) * 1987-08-19 1988-09-15 Heinz Staschel Process for reprocessing fine-grained ferrous by-products from steelworks and metallurgical works to form lumpy material for use in blast furnaces
EP0499779A1 (fr) * 1991-01-24 1992-08-26 Rheinbraun Aktiengesellschaft Procédé de traitement des déchets
DE4324343A1 (de) * 1993-07-20 1995-01-26 Koeppern & Co Kg Maschf Verfahren zum Herstellen von Briketts aus Hüttenreststoffen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 7721, Derwent World Patents Index; Class M24, AN 77-36885Y, XP002010223 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2324081A (en) * 1997-04-07 1998-10-14 Heckett Multiserv Plc Additives for Electric Arc Furnace
US6231634B1 (en) 1997-04-07 2001-05-15 Heckett Multiserv Plc Method for making additives for electric arc furnaces
WO1999028414A3 (fr) * 1997-12-02 1999-09-02 Code Gmbh Procede de refroidissement d'un melange issu d'une reaction exothermique a partir de dechets
GB2337257A (en) * 1998-05-11 1999-11-17 Heckett Multiserv Plc Treating aqueous sludge waste; additives for furnaces
GB2337257B (en) * 1998-05-11 2001-12-12 Heckett Multiserv Plc Making injectable additives for furnaces

Also Published As

Publication number Publication date
AU5159996A (en) 1996-10-23
CA2215409A1 (fr) 1996-10-10
MX9707653A (es) 1998-08-30
JPH11503201A (ja) 1999-03-23
EP0820531A1 (fr) 1998-01-28
AU719637B2 (en) 2000-05-11
BR9604790A (pt) 1998-07-07

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