EP1137818A1 - Procede de traitement thermique de matieres residuelles contenant des metaux lourds - Google Patents

Procede de traitement thermique de matieres residuelles contenant des metaux lourds

Info

Publication number
EP1137818A1
EP1137818A1 EP99957993A EP99957993A EP1137818A1 EP 1137818 A1 EP1137818 A1 EP 1137818A1 EP 99957993 A EP99957993 A EP 99957993A EP 99957993 A EP99957993 A EP 99957993A EP 1137818 A1 EP1137818 A1 EP 1137818A1
Authority
EP
European Patent Office
Prior art keywords
zone
residues
mixture
deck oven
reducing agents
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Withdrawn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
EP99957993A
Other languages
German (de)
English (en)
Inventor
Jean-Luc Roth
Thomas Hansmann
Romain Frieden
Marc Solvi
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.)
Paul Wurth SA
Original Assignee
Paul Wurth SA
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 Paul Wurth SA filed Critical Paul Wurth SA
Publication of EP1137818A1 publication Critical patent/EP1137818A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B9/00—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/10—Making spongy iron or liquid steel, by direct processes in hearth-type furnaces
    • C21B13/105—Rotary hearth-type furnaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/10—Making spongy iron or liquid steel, by direct processes in hearth-type furnaces
    • 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
    • Y02P10/10—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 for the thermal treatment of residues containing heavy metals, e.g. Sludges from surface treatment, pickling and cleaning, metalization and tinning processes of metal parts.
  • residues containing heavy metals e.g. Sludges from surface treatment, pickling and cleaning, metalization and tinning processes of metal parts.
  • the object of the present invention is therefore to propose a method for the thermal treatment of such heavy metal-containing residues.
  • a method for the thermal treatment of residues containing heavy metals in a multi-level furnace which is divided into three zones, each zone having a plurality of superimposed levels and the method comprising the following steps: • Continuous introduction of the heavy metal-containing residues on the top floor of the first zone of the deck oven, the residues being gradually transferred to the second zone and drying while, • Continuous introduction of reducing agents and desulfurization agents onto the top floor of the second zone, the Reducing agent and the desulfurizing agent are mixed with the dried residues, the mixture is heated to approximately 800 ° C. and calcined and gradually transferred to the third zone, • heating the mixture to approximately 1000 ° C. in the third zone, reducing the metals the exhaust gases that arise in this third zone are extracted and treated separately,
  • a major advantage of the invention is that it is possible to reduce and separate the metal oxides, sulfates, chlorides, etc. present as a mixture (in particular iron and zinc), so that the separated fractions are input materials for other processes. In this way, valuable materials can be produced from essential components of the residual materials. After the process has been completed, the iron content can be returned to the production process of a steel mill. Heavy metal oxides are concentrated to such an extent that they can be used as raw materials for the extraction of heavy metals. What remains are ashes, which essentially consist of inert substances such as S.C> 2, Al2O3, MgO, ... and an excess of reducing agents.
  • the heavy metal-containing residues are heated indirectly by heating resistors or directly by burners to approximately 200 ° C., so that the water is completely evaporated and then transferred to the second zone.
  • reducing agent and desulfurizing agent are mixed with the heavy metal-containing residues and this mixture is heated up to approximately 800 ° C., during which the mixture is calcined.
  • the carbonates and sulfates contained in the mixture are decomposed and converted to metal oxides, releasing carbonic acid and sulfur dioxide become.
  • the sulfur dioxide reacts with the desulfurization agents so that the sulfur content in the gases inside the deck furnace remains low.
  • the calcination is complete and the mixture is introduced into the third zone and further heated.
  • the metal oxides begin to react with the reducing agents, whereby the heavy metals evaporate and are discharged together with the exhaust gases from the deck oven.
  • the heavy metals are extracted on the floors in the third zone where they are formed and treated separately from the other exhaust gases. These exhaust gases are then e.g. oxidized in an afterburning chamber, the heavy metals being converted to heavy metal oxides which can then be separated from the exhaust gases in a filter device.
  • the iron oxides remaining in the deck furnace are reduced to metallic iron.
  • the metallic iron produced in this way is removed from the furnace together with the residues of the material introduced, the ashes of the reducing agents and any excess reducing agents that may be present.
  • sludge-like, heavy metal-containing residues can be fed in, whereby caking of the particles is avoided by a targeted process control and by constant circulation.
  • the process delivers a fine-grained end product. This is of particular advantage when ash-forming reducing agents are used. Since the solid end product is fine-grained, it is easy to separate the ash from the iron. This separation can e.g. B. in the hot state via classification.
  • the quality of the directly reduced iron obtained in this way is almost independent of the amount of residues of the reducing agent.
  • the iron obtained can then be processed into briquettes or placed directly in a melting furnace (electric furnace, etc.) and processed further.
  • the resulting residues can be recycled with the unused reducing agents that may be contained in them in a separate gasification reactor, the ash-forming constituents advantageously being separated out as liquid slag and the raw gas formed in the deck oven used as combustion or reducing gas.
  • the charging of reducing agents can also be divided into several stages. There is the possibility that coarse-grained reducing agents (1-3 mm) are introduced further up in the second zone of the deck oven and fine-grained reducing agents ( ⁇ 1 mm) are added below. This largely avoids the discharge of dust with the exhaust gases and accelerates the course of the reaction through the fine reducing agent particles introduced below.
  • the heavy metal-containing residues can, however, also be mixed with - at least some of the required - reducing agents or desulfurizing agents before they are introduced into the deck oven. This is particularly true in the case of treating sludges with a high water content which are mixed with at least some of the reducing agents or desulfurizing agents required before they are introduced into the furnace. This is because the sludge usually has a sticky consistency and, when mixed with a reducing agent or desulfurizing agent, is easier to put in the oven. Mixing with the reducing agents or desulfurizing agents prevents the input material from forming agglomerates when heated.
  • the heavy metal residues are continuously circulated by rakes attached to each floor of the furnace and gradually transported to the floor below.
  • the constant agitation prevents the particles from caking together.
  • the rate of circulation depends on many factors such as. B. the geometry of the rake, the thickness of the layers, etc.
  • the heavy metal residues, any reducing agents and desulfurizing agents on the floors should be circulated at least once every one to three minutes, which largely prevents agglomeration.
  • oxygen-containing gases that have a temperature of at least 250 ° C.
  • a gaseous reducing agent can also be blown in on the bottom floors of the third zone of the deck oven.
  • one or more floors in the furnace, which are below the floor to which reducing agents are introduced are heated by means of a burner.
  • gases are drawn off from the deck oven on each zone on one or more floors.
  • These hot gases can then either be passed through a CO 2 scrubber to reduce the amount of gas and increase the reduction potential of the gas, or can be passed through an additional reactor in which carbon is present, so that the carbon dioxide contained in the hot gases reacts with the carbon to form carbon monoxide according to the Boudoir equilibrium and thereby the reduction potential of the gas is increased.
  • the gases enriched with carbon monoxide are then returned to the deck oven.
  • the Schwerme ⁇ metals can then be sucked off in a relatively small gas quantity on these floors through an outlet in the side wall of the oven.
  • the extracted gas mixture is afterburned, cooled in a cooling device and then cleaned with the aid of a filter before it is released.
  • the deck oven can be operated under a certain excess pressure. In contrast to a rotary kiln, which is sealed over water cups with a diameter of approximately 50 m, this is very easy to achieve in a deck oven that only has small seals on the drive shaft. In such a case, pressure locks must be provided for the input and export of material.
  • Fig. 1 a section through a deck oven for the thermal treatment of residues containing heavy metals.
  • 1 shows a section through a deck oven 10, which consists of three zones 12, 14, 16 lying one below the other, each of which has a plurality of floors 18.
  • These self-supporting levels 18, as well as the jacket 20, the cover 22 and the bottom 24 of the furnace are made of refractory material.
  • each zone 12, 14, 16 there is a suction nozzle 26, 28, 30 through which the gases can be evacuated from the furnace 10.
  • the agbase of the three zones 12, 14, 16 have a different composition so that it makes sense to treat the exhaust gases of the different zones 12, 14, 16 separately.
  • the rakes are designed so that they roll the material inside out on one floor and then outside in on the floor below, so that the material is transported through the furnace from top to bottom.
  • the shaft 34 and the rakes are air-cooled and openings are provided on the rakes through which air can flow into the interior of the furnace and can be used there for afterburning.
  • the residues are applied to the first floor of the first zone 12, while the reducing agents and the desulfurizing agents are fed into the second zone 14 and are brought into contact with the residues containing heavy metals.
  • the heavy metal-containing residues are heated to approximately 200 ° C. and dried.
  • the reducing agents and the desulfurizing agents can be introduced into the furnace.
  • These reducing agents can be in gaseous form or in liquid or solid form.
  • the reducing agents are carbon monoxide, hydrogen, natural gas, petroleum and petroleum derivatives, or solid carbon carriers, such as lignite coke, petroleum coke, blast furnace dust, coal, or the like.
  • the desulfurizing agents contain, for example, lime (CaO), limestone (CaC0 3 ) and / or magnesite (MgO).
  • the reducing agents and the desulfurizing agents which are introduced into the second zone 14 are mixed there by the rakes with the heated, heavy metal-containing residues and heated to approximately 800.degree.
  • the mixture of heavy metal-containing residues, reducing agents and desulfurizing agents is heated to approximately 1000 ° C. Due to the high temperature and the presence of carbon mono- oxide, the oxides contained in the residues are gradually reduced to metal during transport through the deck furnace 10.
  • nozzles 38 are provided for blowing in hot (350 ° C. to 500 ° C.) oxygen-containing gases, through which air or another gas containing oxygen can be introduced into the deck oven 10. Due to the high temperatures and the presence of oxygen, part of the carbon burns to carbon dioxide, which in turn reacts with the excess carbon and is converted to carbon monoxide. The carbon monoxide finally reduces the oxides.
  • burners 40 which ensure a constant high temperature in the levels of the furnace.
  • Gas or coal dust burners can be used here. These burners 40 can be fired with air for preheating and / or for additional heating with gas or coal dust.
  • An additional reducing gas can be generated through the quantitative ratio between oxygen and fuel, or afterburning of the process gases is achieved with excess air.
  • an excess of carbon monoxide can be generated in the burner.
  • With external combustion chambers it can be avoided that the ashes of the burned coal get into the furnace and mix with the iron.
  • the temperatures in the combustion chambers are chosen so that the slag can be drawn off in liquid form and can be disposed of in a glazed form.
  • the production of carbon monoxide reduces the consumption of solid carbon carriers in the furnace 10 and thus also the ash content in the finished product.
  • a gaseous reducing agent for example carbon monoxide or hydrogen
  • the addition of a gaseous reducing agent, for example carbon monoxide or hydrogen, through special nozzles is provided on the last or the last two floors.
  • the reduction of the metal oxides can be completed in this atmosphere with an increased reduction potential.

Landscapes

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

Abstract

L'invention concerne un procédé de traitement thermique de matières résiduelles contenant des métaux lourds dans un four à étages qui est divisé en trois zones, chaque zone présentant plusieurs étages superposés. Ledit procédé comporte les étapes suivantes: amenée en continu des matières résiduelles contenant des métaux lourds sur l'étage supérieur de la première zone du four, les matières résiduelles étant peu à peu transférées dans la seconde zone et séchées pendant ce transfert; amenée en continu d'agents de réduction et d'agents de désulfuration sur l'étage supérieur de la seconde zone, les agents de réduction et les agents de désulfuration étant mélangés avec les matières résiduelles séchées, et le mélange obtenu étant porté à une température d'environ 800 °C et ainsi calciné, puis transféré peu à peu dans la troisième zone; chauffage du mélange jusqu'à une température d'environ 1000 °C dans la troisième zone, les métaux étant réduits, et les effluents gazeux se formant dans cette troisième zone étant aspirés et traités séparément; et extraction du mélange du four à étages.
EP99957993A 1998-11-05 1999-11-04 Procede de traitement thermique de matieres residuelles contenant des metaux lourds Withdrawn EP1137818A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
LU90315A LU90315B1 (de) 1998-11-05 1998-11-05 Verfahren zur thermischen Behandlung schwermetallhaltiger Reststoffe
LU90315 1998-11-05
PCT/EP1999/008439 WO2000028094A1 (fr) 1998-11-05 1999-11-04 Procede de traitement thermique de matieres residuelles contenant des metaux lourds

Publications (1)

Publication Number Publication Date
EP1137818A1 true EP1137818A1 (fr) 2001-10-04

Family

ID=19731781

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99957993A Withdrawn EP1137818A1 (fr) 1998-11-05 1999-11-04 Procede de traitement thermique de matieres residuelles contenant des metaux lourds

Country Status (16)

Country Link
US (1) US6383252B1 (fr)
EP (1) EP1137818A1 (fr)
JP (1) JP2002529597A (fr)
KR (1) KR20010080042A (fr)
CN (1) CN1323359A (fr)
AU (1) AU750943B2 (fr)
BR (1) BR9915309A (fr)
CA (1) CA2345412A1 (fr)
CZ (1) CZ20011548A3 (fr)
LU (1) LU90315B1 (fr)
PL (1) PL348230A1 (fr)
SK (1) SK5962001A3 (fr)
TR (1) TR200101253T2 (fr)
TW (1) TW424004B (fr)
WO (1) WO2000028094A1 (fr)
ZA (1) ZA200102662B (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU90314B1 (de) * 1998-11-05 2000-05-08 Wurth Paul Sa Verfahren zum Herstellen von direkt reduziertem entschwefeltem Eisen
LU90493B1 (de) * 1999-12-23 2001-06-25 Wurth Paul Sa Verfahren zur Verwertung von Kunststoffabfaellen bei der thermischen Behandlung metallhaltiger Reststoffe
US20060213330A1 (en) * 2005-03-22 2006-09-28 Hsieh Chen H Method for recycling metallic sludge
AP2010005222A0 (en) 2007-09-14 2010-04-30 Barrick Gold Corp Process for recovering platinum group metals usingreductants
US8518146B2 (en) 2009-06-29 2013-08-27 Gb Group Holdings Limited Metal reduction processes, metallurgical processes and products and apparatus
AT512739B1 (de) * 2012-04-13 2014-04-15 Andritz Energy & Environment Gmbh Verfahren zur Inertisierung von Schwermetallen wie z.B. sechswertiges Chrom, Chloriden und anderen Salzbildnern sowie löslichen Feststoffen und metallischen Kontaminationen

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US2089782A (en) * 1934-12-14 1937-08-10 Industrimetoder Ab Process of producing sponge iron
US2792298A (en) * 1954-04-09 1957-05-14 Freeman Horace Iron oxide reduction
DE1225673B (de) * 1959-07-23 1966-09-29 Kloeckner Humboldt Deutz Ag Verfahren zur trockenen Reduktion von Eisenerz
US3617256A (en) * 1968-02-28 1971-11-02 Fmc Corp Process for simultaneously producing powdered iron and active carbon
US3756804A (en) * 1972-02-16 1973-09-04 Deltech Inc Process for reclamation of flue dust
US3850613A (en) * 1973-05-14 1974-11-26 Ferro Carb Agglomeration Treatment of steel mill waste dusts containing zinc
AT366718B (de) * 1980-08-08 1982-05-10 Voest Alpine Ag Verfahren zur entzinkung von oxydischen eisentr[gern sowie vorrichtung zur durchfuehrung dieses verfahrens
GB2140141B (en) * 1983-05-20 1986-10-01 British Petroleum Co Plc Process and vacuum sublimation furnace for treatment of ores
DE3564966D1 (en) * 1984-01-26 1988-10-20 Sumitomo Heavy Industries A method for recovering zinc from substances containing a zinc compound

Non-Patent Citations (1)

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Title
See references of WO0028094A1 *

Also Published As

Publication number Publication date
CZ20011548A3 (cs) 2001-10-17
WO2000028094A1 (fr) 2000-05-18
AU750943B2 (en) 2002-08-01
JP2002529597A (ja) 2002-09-10
TR200101253T2 (tr) 2001-09-21
US6383252B1 (en) 2002-05-07
CN1323359A (zh) 2001-11-21
KR20010080042A (ko) 2001-08-22
ZA200102662B (en) 2002-07-01
TW424004B (en) 2001-03-01
LU90315B1 (de) 2000-05-08
SK5962001A3 (en) 2001-12-03
PL348230A1 (en) 2002-05-06
CA2345412A1 (fr) 2000-05-18
AU1551200A (en) 2000-05-29
BR9915309A (pt) 2001-08-07

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