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WO2001054800A1 - Procede de traitement de matieres premieres secondaires metalliferes se trouvant dans un composite combustible - Google Patents

Procede de traitement de matieres premieres secondaires metalliferes se trouvant dans un composite combustible Download PDF

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Publication number
WO2001054800A1
WO2001054800A1 PCT/CH2001/000046 CH0100046W WO0154800A1 WO 2001054800 A1 WO2001054800 A1 WO 2001054800A1 CH 0100046 W CH0100046 W CH 0100046W WO 0154800 A1 WO0154800 A1 WO 0154800A1
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WO
WIPO (PCT)
Prior art keywords
slag
thermal treatment
treatment
flue gas
metal
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/CH2001/000046
Other languages
German (de)
English (en)
Inventor
Serge Biollaz
Rainer Bunge
Martin Schaub
Hans Künstler
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.)
EBERHARD RECYCLING AG
Kuepat AG
Scherrer Paul Institut
VTW Anlagen Schweiz AG
Original Assignee
EBERHARD RECYCLING AG
Kuepat AG
Scherrer Paul Institut
CT Umwelttechnik 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 EBERHARD RECYCLING AG, Kuepat AG, Scherrer Paul Institut, CT Umwelttechnik AG filed Critical EBERHARD RECYCLING AG
Publication of WO2001054800A1 publication Critical patent/WO2001054800A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/73—After-treatment of removed components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
    • B03B9/00—General arrangement of separating plant, e.g. flow sheets
    • B03B9/04—General arrangement of separating plant, e.g. flow sheets specially adapted for furnace residues, smeltings, or foundry slags
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
    • B09B3/35—Shredding, crushing or cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
    • 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
    • C22B7/002—Dry processes by treating with halogens, sulfur or compounds thereof; by carburising, by treating with hydrogen (hydriding)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/006—General arrangement of incineration plant, e.g. flow sheets
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/02—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment
    • F23G5/027—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2202/00—Combustion
    • F23G2202/10—Combustion in two or more stages
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2203/00—Furnace arrangements
    • F23G2203/20—Rotary drum furnace
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2900/00—Special features of, or arrangements for incinerators
    • F23G2900/00001—Exhaust gas recirculation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2700/00—Ash removal, handling and treatment means; Ash and slag handling in pulverulent fuel furnaces; Ash removal means for incinerators
    • F23J2700/001—Ash removal, handling and treatment means
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23L—SUPPLYING AIR OR NON-COMBUSTIBLE LIQUIDS OR GASES TO COMBUSTION APPARATUS IN GENERAL ; VALVES OR DAMPERS SPECIALLY ADAPTED FOR CONTROLLING AIR SUPPLY OR DRAUGHT IN COMBUSTION APPARATUS; INDUCING DRAUGHT IN COMBUSTION APPARATUS; TOPS FOR CHIMNEYS OR VENTILATING SHAFTS; TERMINALS FOR FLUES
    • F23L2900/00—Special arrangements for supplying or treating air or oxidant for combustion; Injecting inert gas, water or steam into the combustion chamber
    • F23L2900/07005—Injecting pure oxygen or oxygen enriched air
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
    • 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 metal-containing secondary raw materials in a combustible composite.
  • the process essentially has three sub-processes: a thermal treatment from which a flue gas / filter ash fraction and a slag fraction are obtained, a flue gas / filter ash preparation and a slag preparation.
  • the process can be used to process, for example, municipal waste, sewage sludge, electronic waste, shredder waste, plastic waste, etc. or mixtures of such waste into reusable metal fractions and reusable mineral fractions.
  • the metals are separated from the residues and, if possible, returned to the material cycle or the metals are more strongly integrated into them by suitable treatment of the residues (glazing) so that they are less are elutable.
  • Metal separation is ecologically more advantageous, because in addition to the recyclable metals, metal-depleted, mineral residues are created that can be used as building materials if necessary.
  • the raw waste is burned or carbonized at low temperature, metals are mechanically separated from the residue from this first incineration or carbonization and the metal-depleted residue is then vitrified at high temperatures, whereby the filter ash can be added and thereby both the non-volatile metals of the combustion residue as well as the volatile metals of the filter ash can be integrated into the glazed slag (Siemens smoldering process, Kubota).
  • Another approach according to the prior art is to extract the heavy metals from the residues by pyrometallurgical methods (metal depletion in the molten state of the slag, e.g. HSR process), resulting in a metal-depleted, glazed slag. If this slag is cooled in a shock-like manner, it develops pozzolanic or latent hydraulic properties and can be used as an additive to hydraulic binders after fine grinding.
  • metal depletion in the molten state of the slag e.g. HSR process
  • the object of the invention is to provide a process for the preparation of secondary raw materials containing heavy metals in a combustible composite.
  • the method according to the invention is not only intended to improve known methods of the same generic type, but is also intended to break new ground in terms of the yield of recyclable heavy metals and in terms of the degree of separation of heavy metals and heavy metal groups in discharged fractions. Nevertheless, the method according to the invention should not be significantly more complex than the known methods and should therefore be able to be carried out using essentially known devices. This object is achieved by the method as defined in the independent claims.
  • the dependent claims define advantageous embodiments of the method.
  • the method according to the invention has three sub-processes: thermal treatment, flue gas / filter ash treatment and slag treatment.
  • Metal fractions metal-rich fractions
  • mineral fractions metal-poor fractions
  • Fractions are achieved by means of a thermal / chemical control of the thermal treatment geared to the separation of the metals and specific methods for the separation of the residues and, if appropriate, by recycling the process to fractions which cannot meet the requirements.
  • the thermal treatment of the process according to the invention is controlled thermally and chemically in such a way that volatile heavy metals (in particular zinc, lead and cadmium) in two stages (reductive metal evaporation stage and metal chloride evaporation stage) to an increased degree in the flue gas compared to the prior art / Filter ash portion are transferred in a form that is suitable for a chemical treatment, for example a thermochemical treatment supported by a hydrochloric acid atmosphere for separating the metals from the filter ash is advantageous.
  • the thermal treatment of the process according to the invention is thermally controlled in such a way that in the slag fraction which arises, in addition to heavy metals which are not volatile (in particular iron, copper, nickel, chromium), cal constituents, these mineral constituents are at least partially melted and vitrified, which essentially enables mechanical processing of the slag fraction into metal fractions and mineral fractions, iron and copper in particular being separable from one another to an increased degree compared to the prior art.
  • the two above-mentioned orientations of the thermal treatment of the method according to the invention for a specific treatment of the filter ash or the slag already bring advantages over the prior art.
  • the two orientations of the thermal treatment can be combined to form a surprisingly simple process in which the advantages with regard to the separation of volatile and non-volatile heavy metals (in particular separation of Zn, Pb, Cd from Fe, Cu, Ni, Cr) and with regard to the separation of the heavy volatile heavy metals (in particular separation of Cu from Fe) in a two-stage thermal treatment, simply without having to remove slag components between the two stages.
  • an at least partially melted slag is created, which after metal depletion can be used as a building material or deposited without any problems.
  • the thermal treatment for the above-mentioned combination is controlled thermally and chemically in such a way that volatile heavy metals pass into the flue gas / filter ash portion as completely as possible, that the mineral slag components are at least partially melted, so that no alloy-like iron-copper compounds are formed, if possible. that the combustible constituents are burned as completely as possible and advantageously also in such a way that the mineral fraction from the slag processing receives pozzolana or latent hydraulic properties and / or can be worked up wet.
  • the thermal treatment must be specified within narrow limits. follow a thermal and chemical profile.
  • the thermal / chemical profile of this thermal treatment essentially has the following characteristics:
  • volatile heavy metals in particular Zn, Pb, Cd
  • the temperature must reach at least approx. 950 ° during this stage and reductive conditions must prevail to prevent oxidation of the metals to be evaporated (conversion into mostly low-volatility compounds and salts).
  • Forming chlorides is necessary stoichiometrically. Temperatures of approx. 900 ° C are necessary for the evaporation of the volatile metal chlorides, above approx. 1100 ° C advantageous. For the evaporation of metal chlorides from the solid phase, it is irrelevant whether there are reductive or oxidative conditions.
  • At least one oxidative stage must be provided with temperatures above approx. 1000 ° C.
  • Slag does not trigger any hydraulic reactions that could lead to the formation of cement stone deposits in the processing plant or to unwanted solidification of the mineral product being applied. Furthermore, the dead burning of the lime prevents a high pH of the leachate from occurring when the dry-mechanically processed, shredded slag is landfilled.
  • features 1 to 6 are necessary and features 7 and 8 are advantageous.
  • Features 1, 2 and 6 are necessary for a process which is only aimed at the volatile heavy metals
  • features 3 to 6 are necessary for a process which is only aimed at the non-volatile heavy metals and features 7 and 8 are advantageous .
  • a chemical treatment for the removal of volatile heavy metals from residues, a chemical treatment, in particular a thermochemical or wet chemical treatment, is used in the process according to the invention.
  • the method already mentioned further above is particularly suitable for a very high degree of separation (EP-0940166, Fluapur).
  • EP-0940166 Fluapur
  • heavy metals are evaporated from residues containing heavy metals in a hydrochloric acid atmosphere and separated from this atmosphere as metal condensate.
  • significantly better separation results can be achieved, in particular for Zn, Pb, and Cd, than with evaporation without hydrochloric acid.
  • the incineration of waste especially municipal waste, usually produces hydrochloric acid (e.g. from PVC), so that the flue gas is already hydrochloric acid.
  • hydrochloric acid gas wash into the aqueous phase and is separated from it by evaporation.
  • hydrochloric acid-containing flue gas and hydrochloric acid from the flue gas scrubber are used for the evaporation of the heavy metals from the corresponding residues.
  • the separation of the slags into fractions with different metal contents which is used in the process according to the invention, has elements of methods for the processing of metallurgical slags.
  • the slag is roughly crushed. Since the vitreous, mineral matrix is brittle, while the metallic parts are ductile, the mineral slag matrix splinters when subjected to mechanical stress, while the metallic parts can be deformed but not crushed. For this reason, the metals accumulate in the coarse fractions and can be separated from the more fine-grained slag, for example by sieving. Such separation processes are known as “selective comminution”.
  • further known processing methods can be used, such as magnetic separation, eddy current sorting and density sorting. Additional metal enrichment or depletion is achieved in the process according to the invention by targeted recycling of fractions with insufficient enrichment or depletion in the process.
  • the metal-depleted fraction of the filter ash treatment is returned to the thermal treatment, which means that it is subjected to a further extraction of volatile heavy metals and may be a welcome supplier of chlorides in the chloride evaporation stage.
  • fractions from the slag processing which have too low a metal content for metal extraction and too high a problem for further use (medium fractions) can be recycled into the fly ash processing or into the thermal treatment.
  • the recyclable products of the process according to the invention are in particular: heavy metal fractions (mainly Zn, Pb, Cd) from filter ash processing, iron metal fractions (mainly Fe), non-ferrous metal fractions (mainly Cu, Ni, Cr) and mineral fractions from slag processing.
  • heavy metal fractions mainly Zn, Pb, Cd
  • iron metal fractions mainly Fe
  • non-ferrous metal fractions mainly Cu, Ni, Cr
  • mineral fractions from slag processing The achievable metal concentrations of the metal fractions are in some cases significantly higher than metal concentrations of natural ores (primary raw materials) and the concentration of heavy metals in the mineral fraction is such that this fraction can be used directly as building materials, for example.
  • the process according to the invention (as in known processes of this type) produces purified flue gas and, if appropriate, wastewater, which are prepared using methods known per se in such a way that they meet the requirements for discharge from the system. Since the method according to the invention is based on a heavy metal-containing secondary raw material in combustible form, for example combustible waste, it also supplies energy to the fractions mentioned or can at least be carried out without external energy.
  • metals can be obtained from secondary raw materials with a significantly higher yield (at least 50% of the metals introduced) than with known methods and this largely independently of
  • Figure 1 is a schematic of the inventive method
  • Figure 2 shows the thermal / chemical profile of the thermal treatment in a preferred embodiment of the inventive method
  • FIG. 3 shows a more detailed diagram of the preferred embodiment of the method according to the invention with a thermal treatment according to FIG. 2.
  • Figure 1 is a diagram of the essential mass flow through the inventive method.
  • the diagram shows the three sub-processes thermal treatment 1, flue gas / filter ash treatment 2 and slag treatment 3 as well as arrows the material flows to and from the sub-processes.
  • the following materials flow to and away from the sub-processes: Entry of the secondary raw material 10 into the thermal treatment 1, flue gas / filter ash portion 11 from the thermal treatment 1 into the flue gas / filter ash preparation 2, slag portion 12 from the thermal treatment 1 in the slag preparation 3, discharge of metal-enriched and metal-depleted fractions 13 and 14 from the flue gas / filter ash treatment 2 and discharge of various metal-enriched or metal-depleted fractions 15, 16 and 17 from the slag treatment.
  • Figures 2 and 3 illustrate a preferred embodiment of the method according to the invention. It is a waste treatment with three-stage incineration (charring, incineration and post-incineration). Figure 2 shows the thermal / chemical profile of the thermal treatment and Figure 3 shows the detailed process scheme.
  • the thermal / chemical profile (FIG. 2) of the thermal treatment of a treatment of municipal waste according to the invention in a three-stage incineration process shows the temperature range (T in ° C.), ranges for the reductive / oxidative conditions ( ⁇ as a proportion of oxygen or combustion air relative) on the stoichiometric need for a combustion of the combustible material) and an exemplary course for the chloride content of the solid phase (f) and the gas phase (g) as a function of the time duration (t) or the location (x) in a continuously operating Investment.
  • the thermal / chemical profile has the features described above for thermal treatment in the method according to the invention and is adapted to three-stage waste incineration (charring, incineration, post-incineration). As already mentioned above, devices for three-stage waste incineration are known and can be adapted accordingly for the thermal treatment according to the method according to the invention. It should be emphasized, however, that this does not limit the method according to the invention to such a three-
  • the thermal / chemical profile according to FIG. 2 has three stages: an initial stage 1.1, a subsequent stage 1.2 and a final stage 1.3.
  • the initial stage 1.1 is a blurring stage, i.e. a stage with sub-stoichiometric combustion (blurring) and therefore reductive conditions ( ⁇ ⁇ 1, advantageously 0.5 to 0.7) and is used by appropriate temperature control (at least temporarily above 950 ° C) also as a metal evaporation stage.
  • This initial stage is advantageously carried out on a grate.
  • the subsequent stage 1.2 is a combustion stage, that is to say a stage with superstoichiometric combustion ( ⁇ > 1, advantageously ⁇ «1.1) and also becomes a chloride evaporation stage by adding chlorides.
  • the chlorides are advantageously added as far as possible in the form of chloride-containing, metal-depleted filter ash during the initial stage 1.1 or at the beginning of the subsequent stage 1.2.
  • the next stage is carried out, for example, in a rotary kiln at temperatures which are between 1100 and 1400 ° C, advantageously between 1200 and 1400 ° C.
  • the conditions for the thermal profile of the process according to the invention are maintained (below the melting point of iron or steel and above the melting temperature of Copper and mineral components, advantageously at temperatures suitable for dead lime) and at least the solid phase can be sufficiently burned out (oxidative stage for the slag component) so that it can be released from the thermal treatment after this stage.
  • the flue gas / filter ash portion is still burned out (oxidative stage for the flue gas / filter ash portion), that is to say completely free of organic compounds and carbon monoxide.
  • This requires oxidative conditions ( ⁇ > 1, advantageously ⁇ »1.5) and temperatures of over 850 ° C are advantageous.
  • the final stage 1.3 is advantageously carried out in an afterburning chamber.
  • FIG. 3 The levels of detail and material flows for a method with the thermal treatment described above, which method represents an exemplary embodiment of the method according to the invention, are shown in FIG. 3 and are described below:
  • the carbonization (initial stage 1.1 of the thermal treatment) is carried out on a grate (material transport from the grate inlet to the grate outlet).
  • the combustible waste 10 secondary raw material
  • air 20.1, enriched air or oxygen, as well as combustible residues 21 from the slag processing 3 and possibly insufficiently enriched fractions 17 from the slag processing and metal-depleted fractions 14 from the ash processing 2.2 are fed in and there is a noxious gas 22, smoldering residue 23 and a first slag fraction 12.1 (rust diarrhea).
  • the charring is carried out according to the thermal / chemical profile of the initial phase 1.1, the reductive conditions being caused by the air supply 20.1 and the temperature also by the air supply 20.1 and possibly additionally by the mass flow rate Support firing, preheating / drying the waste or the air is controlled.
  • the residence time of the waste on the grate is advantageously about 45 minutes.
  • the combustion (subsequent stage 1.2 of the thermal treatment) is carried out in a rotary kiln (material transport from the entrance to the exit). It is supplied with carbon dioxide 22, carbonization residue 23, air 20.2, enriched air or oxygen as well as chloride-containing, metal-depleted residues 14 from the flue gas processing unit, and flue gas 11.1, which still contains organic constituents, and a second slag fraction 12.2 are produced.
  • the combustion is controlled according to the thermal / chemical profile of the subsequent stage 1.2, the oxidative conditions being controlled by the air supply 20.2 and the temperature likewise by the air supply 20.2 and possibly by the supply of carbonization gas 22, by the supply of metal-depleted fractions 14 and / or air preheating is controlled.
  • the residence time of the solid phase in the rotary kiln is advantageously about 45 minutes.
  • the afterburning 1.3 is carried out in an afterburning chamber.
  • the flue gas 11.1 from the combustion, air 20.3 and, if applicable, flue gas 22 from the flue 2 are fed to it and flue gas 11 is produced which no longer has any combustible components.
  • the afterburning is carried out according to the thermal / chemical profile of the final phase 1.3.
  • the air supply regulates the oxidative conditions and the temperature.
  • the slag preparation 3 is carried out essentially according to the selective comminution method described above. It receives the slag fraction 12.1 (rust diarrhea) from the charring 1.1 and the slag fraction 12.2 which has cooled like a shock when it emerges from the rotary kiln from the combustion 1.2, and iron metal fractions 15.1 are formed, Non-ferrous metal fractions 15.2 and mineral fractions 16 as well as possibly insufficiently enriched fractions 17 and wash water 24.
  • slag fraction 12.1 rust diarrhea
  • the slag fraction 12.2 which has cooled like a shock when it emerges from the rotary kiln from the combustion 1.2, and iron metal fractions 15.1 are formed
  • Non-ferrous metal fractions 15.2 and mineral fractions 16 as well as possibly insufficiently enriched fractions 17 and wash water 24.
  • the process of slag processing has a rough crushing and a fine crushing.
  • the slag matrix and fractions of the presorted grate diarrhea which are formed by melting and quenching and consist of little mixed, metallic and mineral areas, are broken, in particular between metallic and mineral areas.
  • the ground slag is separated into mineral components and metal fractions using conventional processing technology.
  • the particle sizes of the fractions obtained in the coarse comminution are approximately 4 mm
  • the flue gas / filter ash treatment 2 essentially has the following steps: an ash separation 2.1, an ash treatment 2.2 and a flue gas cleaning 2.3.
  • the cooled flue gas 11 from the afterburning is separated into solid filter ash 25, which contains the heavy metals and heavy metal chlorides evaporated in the thermal treatment, and pre-cleaned flue gas 26. It is essentially a filtration.
  • the filter ash 25 separated from the flue gas 11, fractions 17 from the slag treatment 3 and, if appropriate, further solid residues such as sludges from the flue gas cleaning are separated into a metal-enriched fraction 13 and a metal-depleted fraction 14.
  • ash treatment 2.2 is supplied, for example, with unpurified (chloride-containing) flue gas 11 from afterburning 1.3 and hydrochloric acid 27 from flue gas cleaning 2.3.
  • a ash-enriched fraction 13, which is discharged from the process, a metal-depleted fraction 14, which is returned to combustion 1.2 or smoldering 1.1, and exhaust gas 28, which is fed into flue gas cleaning 2.3, are produced in ash processing 2.2.
  • the residues treated in ash treatment 2.2 are granulated (granules with particle sizes from 0.5 to 1.5 mm) and in a fluidized bed system or in a rotating tube at temperatures of 850 to 1000 ° C in a hydrochloric acid-containing atmosphere exposed, whereby volatile heavy metals and metal chlorides pass into the gas phase and are separated from this by condensation and filtration.
  • the ash treatment is carried out without an atmosphere containing hydrochloric acid, the ash is optionally added as a solid salt or solution and the ash is treated in a rotary tube or in an annular cracking furnace at temperatures of 850 to 1000 ° C.
  • the pre-cleaned flue gas 26 from the ash separation 2.1 and flue gas 28 from the ash processing unit 2.2 are further cleaned according to methods known per se.
  • Waste water 24 from the slag treatment 3 is also used, and cleaned waste gas 18.1 and waste water 18.2 are produced, which are removed from the process, and hydrochloric acid 27, which is at least partially returned to the ash treatment 2.2.
  • Known dry or quasi-dry exhaust gas purification processes can also be used in which no waste water and no hydrochloric acid are produced.
  • Non-ferrous metal fraction from the slag processing metal content: Cu> 5%
  • Metal fraction from the flue gas treatment Metal contents: Zn> 10%
  • mineral fraction from the slag processing metal content: Cu ⁇ 0.15%, average grain size ⁇ 0.2mm, This fraction contains copper particles with spherical shapes due to melting and iron or steel particles with mechanically created shapes.
  • the fraction may have pozzolana properties due to amorphous silicon oxide and / or contains lime in a burnt state.
  • the mineral fractions of the fractions show microscopic structures from which conclusions can be drawn about the thermal treatment that has gone through.
  • the method according to the invention is characterized in particular by the consistent separation and concentration of heavy metals. This should make it possible to continue using the substances produced, in particular mineral and metallic fractions.
  • the favorable process conditions for heavy metal evaporation and immobilization, as described above also have an advantageous effect on the emissions of organic substances.
  • the improved burnout of the exhaust gas and the mineral residue (C, CO, etc.) should also be emphasized.
  • the very high temperatures also lead to the destruction of dioxins and their precursors.
  • nitrogen oxide emissions the consequent air grading, in addition to heavy metal evaporation, also leads to a significant reduction in nitrogen oxide emissions in the raw gas ( ⁇ 200mg / Nm 3 ).
  • the method according to the invention thus not only has very good properties with regard to the heavy metals but also with regard to organic pollutants.

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Abstract

La présente invention concerne des matières premières secondaires (10), contenant des métaux lourds et se trouvant dans un composite combustible, qui sont recyclées avec un traitement thermique (1), un traitement des gaz de combustion (2) et un traitement des scories (3). Lors du traitement thermique (1), des métaux lourds volatils et des chlorures métalliques volatils, produits par addition de chlorure, sont conduits dans la partie gaz de combustion/cendres de filtre (11), dans des conditions de réduction, par commande thermique et chimique correspondante, les composants minéraux de la partie scories (12) sont au moins partiellement fondus, les parties fer et acier sont laissées à l'état non fondu, afin d'éviter des formations d'alliage, la partie cuivre est fondue et les parties combustibles sont complètement brûlées dans une étape d'oxydation. Des fractions enrichies en métal et appauvries en métal (13, 14, 15, 16, 17) sont produites lors du traitement des gaz de combustion/cendres de filtre (2), à l'aide d'un traitement chimique des cendres de filtre, par exemple dans une atmosphère contenant de l'acide chlorhydrique, et lors du traitement des scories (3), par broyage et fractionnement mécaniques. L'addition de chlorure pour le traitement thermique (1) est de préférence réalisée par remise en circulation de la fraction appauvrie en métal (14), qui est issue du traitement des gaz de combustion/cendres de filtre (2). Les fractions issues du traitement des scories (3) qui présentent un enrichissement en métal insuffisant sont remises en circulation dans le traitement thermique (1) ou dans le traitement des gaz de combustion/cendres de filtre (3). Les fractions enrichies en métal, issues du procédé, peuvent être soumises à une récupération de métal et les fractions appauvries en métal peuvent être utilisées en tant que matériaux de construction présentant éventuellement des propriétés puzzolaniques ou hydrauliques latentes.
PCT/CH2001/000046 2000-01-25 2001-01-25 Procede de traitement de matieres premieres secondaires metalliferes se trouvant dans un composite combustible Ceased WO2001054800A1 (fr)

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CN101979944A (zh) * 2010-11-02 2011-02-23 郭继中 挥发性金属焙烧回收装置
EP2375153A1 (fr) * 2010-04-12 2011-10-12 Heiner Zwahr Préparation de cendres volantes
CN101716553B (zh) * 2009-12-28 2012-04-18 河南理工大学 一种锌挥发窑窑渣加工工艺
DE102012004455A1 (de) * 2012-03-08 2013-09-12 Andreas Ermke Verfahren und Vorrichtung zur thermischen Vernichtung von elektronischen Datenträgern
CN103551244A (zh) * 2013-11-21 2014-02-05 河北联合大学 高炉絮凝尘泥回收有价元素的方法
JP2017127797A (ja) * 2016-01-18 2017-07-27 メタウォーター株式会社 汚泥の焼却システム
DE102017110474A1 (de) * 2017-05-15 2018-11-15 Ecoenergy Gesellschaft Für Energie- Und Umwelttechnik Mbh Verfahren zur Entfernung von organischen und anorganischen Schadstoffen aus Abfällen mittels nassmechanischer Trennung
CN109261347A (zh) * 2018-09-05 2019-01-25 云南省环境科学研究院(中国昆明高原湖泊国际研究中心) 一种铅锌冶炼废渣资源化利用的方法
CN112058868A (zh) * 2020-08-31 2020-12-11 青海北辰科技有限公司 一种电解镁生产中固体废渣的处理装置
CN112536154A (zh) * 2020-09-03 2021-03-23 中南大学 一种浮选分离微细粒铅氧化合物与铁氧化合物的药剂组及其应用
CN112853112A (zh) * 2021-01-09 2021-05-28 中新国际联合研究院 一种实现全回收铬渣中铬的方法
CN113088709A (zh) * 2021-03-30 2021-07-09 攀钢集团攀枝花钢铁研究院有限公司 同步分离烧结机头灰中钾、铅、铁的方法
WO2021190026A1 (fr) * 2020-03-24 2021-09-30 鑫联环保科技股份有限公司 Système de capture de métal lourd semi-volatil dans des déchets solides contenant du zinc par séparation à haute température associée à une complexation par l'ammonium
CN114951207A (zh) * 2022-04-29 2022-08-30 中国地质大学（北京） 一种高铁高炉灰资源材料化全利用方法
CN115560336A (zh) * 2022-10-13 2023-01-03 广东广业投资集团有限公司 危废焚烧灰渣在线熔融系统、方法及路基材料

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FR2716392A1 (fr) * 1994-02-22 1995-08-25 Commissariat Energie Atomique Extraction de métaux lourds contenus dans les cendres volantes et les résidus d'épuration des fumées issues d'un four d'incinération.
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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101716553B (zh) * 2009-12-28 2012-04-18 河南理工大学 一种锌挥发窑窑渣加工工艺
EP2375153A1 (fr) * 2010-04-12 2011-10-12 Heiner Zwahr Préparation de cendres volantes
US8349282B2 (en) 2010-04-12 2013-01-08 Green Conversion Systems, Llc Treatment of fly ash
CN101979944A (zh) * 2010-11-02 2011-02-23 郭继中 挥发性金属焙烧回收装置
CN101979944B (zh) * 2010-11-02 2012-07-18 郭继中 挥发性金属焙烧回收装置
DE102012004455A1 (de) * 2012-03-08 2013-09-12 Andreas Ermke Verfahren und Vorrichtung zur thermischen Vernichtung von elektronischen Datenträgern
DE102012004455B4 (de) * 2012-03-08 2014-01-09 Andreas Ermke Verfahren und Vorrichtung zur thermischen Vernichtung von elektronischen Datenträgern
CN103551244A (zh) * 2013-11-21 2014-02-05 河北联合大学 高炉絮凝尘泥回收有价元素的方法
JP2017127797A (ja) * 2016-01-18 2017-07-27 メタウォーター株式会社 汚泥の焼却システム
WO2018210379A1 (fr) 2017-05-15 2018-11-22 Ecoenergy Gesellschaft Für Energie- Und Umwelttechnik Mbh Procédé pour éliminer des substances nocives organiques ou inorganiques de déchets au moyen d'une séparation gravimétrique
DE102017110474A1 (de) * 2017-05-15 2018-11-15 Ecoenergy Gesellschaft Für Energie- Und Umwelttechnik Mbh Verfahren zur Entfernung von organischen und anorganischen Schadstoffen aus Abfällen mittels nassmechanischer Trennung
CN109261347A (zh) * 2018-09-05 2019-01-25 云南省环境科学研究院(中国昆明高原湖泊国际研究中心) 一种铅锌冶炼废渣资源化利用的方法
CN109261347B (zh) * 2018-09-05 2020-04-21 云南省环境科学研究院(中国昆明高原湖泊国际研究中心) 一种铅锌冶炼废渣资源化利用的方法
WO2021190026A1 (fr) * 2020-03-24 2021-09-30 鑫联环保科技股份有限公司 Système de capture de métal lourd semi-volatil dans des déchets solides contenant du zinc par séparation à haute température associée à une complexation par l'ammonium
CN112058868A (zh) * 2020-08-31 2020-12-11 青海北辰科技有限公司 一种电解镁生产中固体废渣的处理装置
CN112536154A (zh) * 2020-09-03 2021-03-23 中南大学 一种浮选分离微细粒铅氧化合物与铁氧化合物的药剂组及其应用
CN112536154B (zh) * 2020-09-03 2022-06-14 中南大学 一种浮选分离微细粒铅氧化合物与铁氧化合物的药剂组及其应用
CN112853112A (zh) * 2021-01-09 2021-05-28 中新国际联合研究院 一种实现全回收铬渣中铬的方法
CN113088709A (zh) * 2021-03-30 2021-07-09 攀钢集团攀枝花钢铁研究院有限公司 同步分离烧结机头灰中钾、铅、铁的方法
CN114951207A (zh) * 2022-04-29 2022-08-30 中国地质大学（北京） 一种高铁高炉灰资源材料化全利用方法
CN115560336A (zh) * 2022-10-13 2023-01-03 广东广业投资集团有限公司 危废焚烧灰渣在线熔融系统、方法及路基材料
CN115560336B (zh) * 2022-10-13 2023-06-16 广东广业投资集团有限公司 危废焚烧灰渣在线熔融系统、方法及路基材料

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