CA2216714A1 - Process for the separation of copper and heavy metals from incinerated garbage residue and slag - Google Patents
Process for the separation of copper and heavy metals from incinerated garbage residue and slag Download PDFInfo
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- CA2216714A1 CA2216714A1 CA002216714A CA2216714A CA2216714A1 CA 2216714 A1 CA2216714 A1 CA 2216714A1 CA 002216714 A CA002216714 A CA 002216714A CA 2216714 A CA2216714 A CA 2216714A CA 2216714 A1 CA2216714 A1 CA 2216714A1
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- slag
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- chlorides
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B3/00—General features in the manufacture of pig-iron
- C21B3/04—Recovery of by-products, e.g. slag
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- 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
- C22B1/02—Roasting processes
- C22B1/08—Chloridising roasting
-
- 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
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/08—Toxic combustion residues, e.g. toxic substances contained in fly ash from waste incineration
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
- A62D2203/02—Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40
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- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- General Health & Medical Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Health & Medical Sciences (AREA)
- Emergency Management (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Geochemistry & Mineralogy (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
In a process for the separation of copper and heavy metals from incinerated garbage residue and slag, the residue and slag from garbage incineration or pyrolysis is heated to over 650 ~C under reducing conditions together with substances containing chlorine or chlorides, such as flue gas cleaning residues, CaCl2 from the soda production, cooking salt, organic solvents or electroplating sludge containing chlorine, whereupon Cu-chlorides and volatile heavy metal chlorides, such as PbCl2 or ZnCl2, are drawn off in the gas phase.
Description
Method ~or Se~aratina Co~er and Heavy Metals from Waste Incineration Residues and Sla~s The invention relates to a method ~or separating copper and heavy metals from waste incineration residues and slags.
In conventional waste incineration plants as well as waste pyrolysis plants, residues in the form of pyrolysis residues or waste incineration residues or slags incur. As a rule, such slags are relatively acidic and, depending on the provenance of the waste and, in particular, when using industrial waste, such slags mostly are strongly cont~min~ted with heavy metals.
The direct utilization of such slags without more or less intensive purification is feasible only at high apparative expenditures.
The invention aims at rendering such heavy-metal-containing waste incineration residues suitable for subsequent processing by which, ~or instance, in respect of steel slags environ-mentally compatible hydraulic binders or other valuable sub-stances may be recovered A slag not directly suitable for metallurgical processes or residues of the above type, in particular, are to be processable to synthetic blast furnace slag having hydraulic properties as well as high-quality carbon-saturated iron alloys. To solve this object, the method according to the invention essentially consists in that the waste incineration and/or pyrolysis residues and slags, together with chlorine and/or chloride-cont~ining substances, such as smoke gas purification residues, CaCl2 ~rom soda production, common salt, chlorine-containing organic solvents or sludges derived from electroplating, are heated to above 650~C under reducing conditions, whereupon Cu chlorides and volatile heavy metal chlorides, such as, e.g., PbCl2 or ZnCl2, are drawn off in the gaseous phase. The fact that the waste incineration residues and slags and/or pyrolysis residues are calcined along with chlorine and/or chloride-containing substances while maintaining reducing conditions during such roasting allows for the separation of heavy metals in the form o~ volatile chlorides and the discharging of the same via the gaseous phase. The gaseous phase may be purified in a conventional manner, wherein copper, chloride, bleaching chloride and zinc chloride may be quantitatively retained by filters. At the same time, a method of this type allows for also the working up of other products that are difficult to dispose o~, such as chlorine-containing organic solvents as well as smoke gas purification residues or calcium chloride from soda production, wherein, on the whole, a great number o~
problem substances can be disposed of simultaneously. In principle, the heavy metal chlorides mentioned have relatively low vapour pressures at low temperatures. The vapour pressures of relevant heavy metal chlorides at 600~C are as follows:
Component Vapour pressure (bar) CuC12, (CuC1)2 0 005 PbCl2 0.07 ZnC12 0.1 In order to ensure safe volatilization at relatively low temperatures, the respective partial pressure must be appropriately lowered, for instance by using a flush gas, or operation must be effected under an at least partial vacuum Advantageously, the method according to the invention is realized in a manner that flush gases, in particular hot combustion offgases, are used at temperatures of between 650~
and 1400~ C for discharging the volatile chlorides, thus causing a sufficient volatilization of the heavy meta]
chlorides to be observed. Alternatively, or in addition to using such a flush gas, operation may also take place in a partially evacuated shaft furnace or a flush gas may be employed at a negative pressure. At a pressure of 1 bar and without using a flush gas, chlorination would have to be effected at temperatures of approximately 1400~C, i.e., at melting temperature.
By the measure taken according to the invention a su~ficiently high depletion o~ heavy metals is ensured in conventional shaft furnaces by means of combustion offgases used as a flush gas, already at temperatures of 850~C, it being advantageously proceeded in a manner that heating o~ the waste incineration residues and slags to temperatures of approximately 850~C is e~ected in a sha~t ~urnace or in a rotary tubular kiln The recovery of heavy metals from the gaseous phase may be e~ected in a particularly simple manner by conducting the gaseous phase containing the volatile heavy metal chlorides through a filter and dissolving in water, and/or cementing with iron scrap, the heavy-metal-chloride-containing ~ilter dust, whereupon the heavy-metal chlorides are extracted and/or the heavy metals are separated by fractional electrolysis and/or are ~ractionally distilled. During the cementation with iron scrap the heavy metal oxides are reduced and iron chloride is ~ormed During the fractional electrolysis copper, tin, nickel and other metals may be separated individually and in high purities.
In order to ensure the partial pressures required while, at the same time, maintaining reducing conditions, it is advantageously proceeded in a manner that heating is e~ected in a shaft furnace by means of combustion o~gases in countercurrent.
Particularly reasonable ~urther processing from an economic point of view, of the appropriately depleted waste incin-eration or pyrolysis residues and slags is feasible if, as inaccordance with a pre~erred further development, the heated solid residues are mixed with liquid steel slag or lime marl in amounts of from 10 to 40 % by weight, preferably about 20 %
by weight, so as to form a mixed slag, wherein evaporating heavy metals that have remained, such as Pb and Zn, are separated ~rom the gaseous phase and chlorides possibly dissolved in the mixed slag, such as, e.g., CaCl2, are oxidized under Cl2 stripping and the mixed slag is reduced above a turbulent Fe bath having a C content ranging between 3 and 4 % by weight. Since the heated residues enter into an acid reaction, it is feasible by mixing with steel slag to at least partially neutralize the extremely basic steel slag, the viscosity being lowered simultaneously. The mixing and neutralization heat allows for the safe evaporation of heavy metals possibly still left At the same time, an iron bath is sedimented out of the steel slag, it being advantageousl~
proceeded in a manner that the turbulent Fe bath is subjected to a fractional reduction for separating a ferro-chromiurn alloy. In doing so, the turbulent iron bath must be maintained at the required carbon content of between 3 and 4 % by weight in order to ensure that the desired reduction does actually take place, wherein a total of I ton synthetic blast furnace slag and 0.9 ton pig iron may, for instance, be obtained from approximately 0.4 ton calcined slag and 1.6 tons of steel slag. In order to ensure the formation of a suitable cement aggregate, chlorides must be stripped first.
The method for reducingly calcining waste incineration residues and slags in a particularly advantageous manner thus may be combined with an appropriate method for producing synthetic blast furnace slag, since the CO formed on account of the carbon contents required in the iron bath may be utilized particularly well from an energetic point of view. To this end, it is advantageously proceeded in a manner that the CO formed in the reduction of the slag mixture by the carbon dissolved in the Fe bath is used for further burning and heating the mixed slag and/or the residues.
In order to further enhance the quality of the synthetic blast furnace slag and to be able to produce particularly suitable cement aggregates or cement directly, it is advantageously proceeded in a manner that bauxite, or A12O3, is added to the liquid mixed slag.
As already mentioned in the beginning, the partial pressures required ~or the volatile chlorides may be ad]usted either by suitable amounts of flush gas or by applying a subatmospheric pressure.
In the following the invention will be explained in more detail by way of an exemplary embodiment.
A waste slag having the following composition Component Portion (~) SiO2 43 CaO 13 Al2~3 8.5 Fe203 10 MgO 1 5 Na2O 3.5 TiO2 1 5 Cu 0.4 Ni 0 04 Cr 0.15 Zn 0.35 Pb 0.15 was used. The balance of the analysis in this case comprises unburnt matter and waste scrap.
A waste slag of this type was charged into a shaft furnace along with 10 % CaCl2 (3.6 % Ca + 6.4 % Cl) and heated at an oxygen shortage (countercurrent) by reduced operation. The offgas temperature of the shaft amounted to about 850~C. The calcined molten waste slag had the following analysis:
Component Portion (~) SiO2 54 CaO 21 Fe2O3 4 MgO 2 Na2O 3 SO3 0.5 Tio2 1.5 Cu 0.08 Ni 0.02 Cr 0.2 Zn 0.06 Pb 0.04 The calcined waste slag was mixed with 80 % steel slag in the liquid state, thejlatter having the following composition:
Component Portion (%) Steel 24 sio2 13 CaO 33 MgO 4 FeO 21 S 0.05 p 0.5 Cr The mixed slag had the ~ollowing composition:
Component Portion (%) Steel 20 SiO2 21 CaO 31 Al2O3 3 FeO 18 MgO 3-5 Na2O 0.6 SO3 0.15 Tio2 0.3 Cu 0.016 Ni 0.004 Cr 0 9 During the mixing procedure Zn and Pb evaporate practically quantitatively and could be recovered ~rom the o~gas.
That mixed slag was reduced in an OBM converter above a turbulent iron bath by means o~ carbon dissolved in the iron bath. The reduction heat as well as the waste heat losses in the gaseous phase were fed to the process very economically by partially burning the ~ormed CO in the upper part o~ the converter.
The reduced slag had the ~ollowing composition:
Component . Portion (%) SiO2 35 CaO 52 Al2~3 5 MgO 5 Na20 SO3 0.25 TiO2 0-5 Cr 0.03 The heavy metals Cu and Ni no longer were detectable in the reduced slag by means o~ X-ray ~luorescence analysis (detection limit approx. 100 ppm).
The water-spray granulated slag proved to be a readily hydraulically active mixed cement component. Approximately 10 % bauxite (Al203) was added to the liquid slag melt with a view to providing a mixed cement having an elevated early strength.
The regulus (pig iron) obtained had the following composition:
Component Portion (%) Cu 0 05 Ni 0.01 Cr 2.6 ,C 3.8 Fe balance The method was conducted in a manner that the carbon portion of the iron bath always ranged between 3 and 4 ~ by weight.
The pig iron thus obtained constitutes a high-quality charging substance for the steel industry. Alternatively, a carbon-~ree, highly enriched ferro-chromium alloy may, in turn, be obtained by fractional reduction.
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In conventional waste incineration plants as well as waste pyrolysis plants, residues in the form of pyrolysis residues or waste incineration residues or slags incur. As a rule, such slags are relatively acidic and, depending on the provenance of the waste and, in particular, when using industrial waste, such slags mostly are strongly cont~min~ted with heavy metals.
The direct utilization of such slags without more or less intensive purification is feasible only at high apparative expenditures.
The invention aims at rendering such heavy-metal-containing waste incineration residues suitable for subsequent processing by which, ~or instance, in respect of steel slags environ-mentally compatible hydraulic binders or other valuable sub-stances may be recovered A slag not directly suitable for metallurgical processes or residues of the above type, in particular, are to be processable to synthetic blast furnace slag having hydraulic properties as well as high-quality carbon-saturated iron alloys. To solve this object, the method according to the invention essentially consists in that the waste incineration and/or pyrolysis residues and slags, together with chlorine and/or chloride-cont~ining substances, such as smoke gas purification residues, CaCl2 ~rom soda production, common salt, chlorine-containing organic solvents or sludges derived from electroplating, are heated to above 650~C under reducing conditions, whereupon Cu chlorides and volatile heavy metal chlorides, such as, e.g., PbCl2 or ZnCl2, are drawn off in the gaseous phase. The fact that the waste incineration residues and slags and/or pyrolysis residues are calcined along with chlorine and/or chloride-containing substances while maintaining reducing conditions during such roasting allows for the separation of heavy metals in the form o~ volatile chlorides and the discharging of the same via the gaseous phase. The gaseous phase may be purified in a conventional manner, wherein copper, chloride, bleaching chloride and zinc chloride may be quantitatively retained by filters. At the same time, a method of this type allows for also the working up of other products that are difficult to dispose o~, such as chlorine-containing organic solvents as well as smoke gas purification residues or calcium chloride from soda production, wherein, on the whole, a great number o~
problem substances can be disposed of simultaneously. In principle, the heavy metal chlorides mentioned have relatively low vapour pressures at low temperatures. The vapour pressures of relevant heavy metal chlorides at 600~C are as follows:
Component Vapour pressure (bar) CuC12, (CuC1)2 0 005 PbCl2 0.07 ZnC12 0.1 In order to ensure safe volatilization at relatively low temperatures, the respective partial pressure must be appropriately lowered, for instance by using a flush gas, or operation must be effected under an at least partial vacuum Advantageously, the method according to the invention is realized in a manner that flush gases, in particular hot combustion offgases, are used at temperatures of between 650~
and 1400~ C for discharging the volatile chlorides, thus causing a sufficient volatilization of the heavy meta]
chlorides to be observed. Alternatively, or in addition to using such a flush gas, operation may also take place in a partially evacuated shaft furnace or a flush gas may be employed at a negative pressure. At a pressure of 1 bar and without using a flush gas, chlorination would have to be effected at temperatures of approximately 1400~C, i.e., at melting temperature.
By the measure taken according to the invention a su~ficiently high depletion o~ heavy metals is ensured in conventional shaft furnaces by means of combustion offgases used as a flush gas, already at temperatures of 850~C, it being advantageously proceeded in a manner that heating o~ the waste incineration residues and slags to temperatures of approximately 850~C is e~ected in a sha~t ~urnace or in a rotary tubular kiln The recovery of heavy metals from the gaseous phase may be e~ected in a particularly simple manner by conducting the gaseous phase containing the volatile heavy metal chlorides through a filter and dissolving in water, and/or cementing with iron scrap, the heavy-metal-chloride-containing ~ilter dust, whereupon the heavy-metal chlorides are extracted and/or the heavy metals are separated by fractional electrolysis and/or are ~ractionally distilled. During the cementation with iron scrap the heavy metal oxides are reduced and iron chloride is ~ormed During the fractional electrolysis copper, tin, nickel and other metals may be separated individually and in high purities.
In order to ensure the partial pressures required while, at the same time, maintaining reducing conditions, it is advantageously proceeded in a manner that heating is e~ected in a shaft furnace by means of combustion o~gases in countercurrent.
Particularly reasonable ~urther processing from an economic point of view, of the appropriately depleted waste incin-eration or pyrolysis residues and slags is feasible if, as inaccordance with a pre~erred further development, the heated solid residues are mixed with liquid steel slag or lime marl in amounts of from 10 to 40 % by weight, preferably about 20 %
by weight, so as to form a mixed slag, wherein evaporating heavy metals that have remained, such as Pb and Zn, are separated ~rom the gaseous phase and chlorides possibly dissolved in the mixed slag, such as, e.g., CaCl2, are oxidized under Cl2 stripping and the mixed slag is reduced above a turbulent Fe bath having a C content ranging between 3 and 4 % by weight. Since the heated residues enter into an acid reaction, it is feasible by mixing with steel slag to at least partially neutralize the extremely basic steel slag, the viscosity being lowered simultaneously. The mixing and neutralization heat allows for the safe evaporation of heavy metals possibly still left At the same time, an iron bath is sedimented out of the steel slag, it being advantageousl~
proceeded in a manner that the turbulent Fe bath is subjected to a fractional reduction for separating a ferro-chromiurn alloy. In doing so, the turbulent iron bath must be maintained at the required carbon content of between 3 and 4 % by weight in order to ensure that the desired reduction does actually take place, wherein a total of I ton synthetic blast furnace slag and 0.9 ton pig iron may, for instance, be obtained from approximately 0.4 ton calcined slag and 1.6 tons of steel slag. In order to ensure the formation of a suitable cement aggregate, chlorides must be stripped first.
The method for reducingly calcining waste incineration residues and slags in a particularly advantageous manner thus may be combined with an appropriate method for producing synthetic blast furnace slag, since the CO formed on account of the carbon contents required in the iron bath may be utilized particularly well from an energetic point of view. To this end, it is advantageously proceeded in a manner that the CO formed in the reduction of the slag mixture by the carbon dissolved in the Fe bath is used for further burning and heating the mixed slag and/or the residues.
In order to further enhance the quality of the synthetic blast furnace slag and to be able to produce particularly suitable cement aggregates or cement directly, it is advantageously proceeded in a manner that bauxite, or A12O3, is added to the liquid mixed slag.
As already mentioned in the beginning, the partial pressures required ~or the volatile chlorides may be ad]usted either by suitable amounts of flush gas or by applying a subatmospheric pressure.
In the following the invention will be explained in more detail by way of an exemplary embodiment.
A waste slag having the following composition Component Portion (~) SiO2 43 CaO 13 Al2~3 8.5 Fe203 10 MgO 1 5 Na2O 3.5 TiO2 1 5 Cu 0.4 Ni 0 04 Cr 0.15 Zn 0.35 Pb 0.15 was used. The balance of the analysis in this case comprises unburnt matter and waste scrap.
A waste slag of this type was charged into a shaft furnace along with 10 % CaCl2 (3.6 % Ca + 6.4 % Cl) and heated at an oxygen shortage (countercurrent) by reduced operation. The offgas temperature of the shaft amounted to about 850~C. The calcined molten waste slag had the following analysis:
Component Portion (~) SiO2 54 CaO 21 Fe2O3 4 MgO 2 Na2O 3 SO3 0.5 Tio2 1.5 Cu 0.08 Ni 0.02 Cr 0.2 Zn 0.06 Pb 0.04 The calcined waste slag was mixed with 80 % steel slag in the liquid state, thejlatter having the following composition:
Component Portion (%) Steel 24 sio2 13 CaO 33 MgO 4 FeO 21 S 0.05 p 0.5 Cr The mixed slag had the ~ollowing composition:
Component Portion (%) Steel 20 SiO2 21 CaO 31 Al2O3 3 FeO 18 MgO 3-5 Na2O 0.6 SO3 0.15 Tio2 0.3 Cu 0.016 Ni 0.004 Cr 0 9 During the mixing procedure Zn and Pb evaporate practically quantitatively and could be recovered ~rom the o~gas.
That mixed slag was reduced in an OBM converter above a turbulent iron bath by means o~ carbon dissolved in the iron bath. The reduction heat as well as the waste heat losses in the gaseous phase were fed to the process very economically by partially burning the ~ormed CO in the upper part o~ the converter.
The reduced slag had the ~ollowing composition:
Component . Portion (%) SiO2 35 CaO 52 Al2~3 5 MgO 5 Na20 SO3 0.25 TiO2 0-5 Cr 0.03 The heavy metals Cu and Ni no longer were detectable in the reduced slag by means o~ X-ray ~luorescence analysis (detection limit approx. 100 ppm).
The water-spray granulated slag proved to be a readily hydraulically active mixed cement component. Approximately 10 % bauxite (Al203) was added to the liquid slag melt with a view to providing a mixed cement having an elevated early strength.
The regulus (pig iron) obtained had the following composition:
Component Portion (%) Cu 0 05 Ni 0.01 Cr 2.6 ,C 3.8 Fe balance The method was conducted in a manner that the carbon portion of the iron bath always ranged between 3 and 4 ~ by weight.
The pig iron thus obtained constitutes a high-quality charging substance for the steel industry. Alternatively, a carbon-~ree, highly enriched ferro-chromium alloy may, in turn, be obtained by fractional reduction.
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Claims (10)
1. A method for separating copper and heavy metals from waste incineration residues and slags, characterized in that the waste incineration and/or pyrolysis residues and slags, together with chlorine and/or chloride-containing substances, such as smoke gas purification residues, CaCl2 from soda production, common salt, chlorine-containing organic solvents or sludges derived from electroplating, are heated to above 650°C under reducing conditions, whereupon Cu chlorides and volatile heavy metal chlorides, such as, e.g., PbCl2 or ZnCl2, are drawn off in the gaseous phase.
2. A method according to claim 1, characterized in that flush gases, in particular hot combustion offgases, are used at temperatures of between 650° and 1400° C for discharging the volatile chlorides.
3. A method according to claim 1 or 2, characterized in that the gaseous phase containing the volatile heavy metal chlorides are conducted via a filter and the heavy-metal-chloride-containing filter dust is dissolved in water and/or cemented with Fe scrap, whereupon the heavy-metal chlorides are extracted and/or the heavy metals are separated by fractional electrolysis and/or are fractionally distilled.
4. A method according to claim 1, 2 or 3, characterized in that heating is effected in a shaft furnace by means of combustion offgases in countercurrent
5. A method according to any one of claims 1 to 4, characterized in that the heated solid residues are mixed with liquid steel slag or lime marl in amounts of from 10 to 40 %
by weight, preferably about 20 % by weight, so as to form a mixed slag, wherein evaporating heavy metals that have remained, such as Pb and Zn, are separated from the gaseous phase and chlorides possibly dissolved in the mixed slag, such as, e.g., CaCl2, are oxidized under Cl2 stripping and the mixed slag is reduced above a turbulent Fe bath having a C
content ranging between 3 and 4 % by weight.
by weight, preferably about 20 % by weight, so as to form a mixed slag, wherein evaporating heavy metals that have remained, such as Pb and Zn, are separated from the gaseous phase and chlorides possibly dissolved in the mixed slag, such as, e.g., CaCl2, are oxidized under Cl2 stripping and the mixed slag is reduced above a turbulent Fe bath having a C
content ranging between 3 and 4 % by weight.
6. A method according to any one of claims 1 to 5, characterized in that the turbulent Fe bath is subjected to a fractional reduction for separating a ferro-chromium alloy.
7. A method according to any one of claims 1 to 6, characterized in that heating of the residues to temperatures of approximately 850°C is effected in a shaft furnace or in a rotary tubular kiln.
8. A method according to any one of claims 1 to 7, characterized in that the CO formed in the reduction of the mixed slag by the carbon dissolved in the Fe bath is used for further burning and heating the mixed slag and/or the residues.
9. A method according to any one of claims 1 to 8, characterized in that bauxite, or Al2O3, is added to the liquid mixed slag.
10. A method according to any one of claims 1 to 9, characterized in that heating is effected under subatmospheric pressure.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ATA233/96 | 1996-02-08 | ||
| AT0023396A AT405191B (en) | 1996-02-08 | 1996-02-08 | METHOD FOR SEPARATING COPPER AND HEAVY METALS FROM WASTE COMBUSTION RESIDUES AND SLAGS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2216714A1 true CA2216714A1 (en) | 1997-08-14 |
Family
ID=3485101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002216714A Abandoned CA2216714A1 (en) | 1996-02-08 | 1997-02-05 | Process for the separation of copper and heavy metals from incinerated garbage residue and slag |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0820532A1 (en) |
| AT (1) | AT405191B (en) |
| CA (1) | CA2216714A1 (en) |
| CZ (1) | CZ305897A3 (en) |
| HR (1) | HRP970030B1 (en) |
| HU (1) | HUP9901450A2 (en) |
| SK (1) | SK132497A3 (en) |
| WO (1) | WO1997029214A1 (en) |
| ZA (1) | ZA971032B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL123068A (en) * | 1998-01-26 | 2001-05-20 | Rosenberg Ariel | High efficiency recovery process for treatment of multi-element waste |
| WO2001054800A1 (en) * | 2000-01-25 | 2001-08-02 | Paul Scherrer Institut | Method for processing metalliferous secondary raw materials in a combustible composite |
| AT502396B1 (en) * | 2005-09-01 | 2007-03-15 | Montanuniv Leoben | METHOD FOR REMOVING CONTAMINANTS FROM INGREDIENTS |
| GB0900677D0 (en) | 2009-01-16 | 2009-02-25 | Minex Technologies Ltd | Metal recovery process |
| RU2484868C2 (en) * | 2009-04-24 | 2013-06-20 | Ольга Анатольевна Афанасьевская | Complex wasteless treatment of toxic wastes |
| DE102017110474A1 (en) * | 2017-05-15 | 2018-11-15 | Ecoenergy Gesellschaft Für Energie- Und Umwelttechnik Mbh | Process for the removal of organic and inorganic pollutants from waste by wet mechanical separation |
| CN108193046B (en) * | 2018-02-23 | 2019-08-20 | 马鞍山市伟泰锡业有限公司 | The optimal recovery method of metal in a kind of tin anode mud |
| CN115679109B (en) * | 2022-11-14 | 2024-04-09 | 中南大学 | Method for selectively recycling heavy metals in copper smelting smoke dust |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE444612C (en) * | 1925-07-24 | 1927-05-24 | Victor Tafel Dr Ing | Extraction of copper, lead, zinc, silver, etc. from poor ores |
| NL7710901A (en) * | 1977-10-05 | 1979-04-09 | Esmil B V Stationsstraat 48 | PROCESS FOR THE SIMULTANEOUS PROCESSING OF USED METAL AND / OR METAL WASTE FROM HALOGENATED HYDROCARBONS. |
| US5276250A (en) * | 1986-07-11 | 1994-01-04 | Hagenmaier Hans Paul | Process for decomposing polyhalogenated compounds |
| US5245120A (en) * | 1991-12-27 | 1993-09-14 | Physical Sciences, Inc. | Process for treating metal-contaminated materials |
| CH683676A5 (en) * | 1992-05-12 | 1994-04-29 | Holderbank Financ Glarus | A method for treating waste incineration residues to a sustainable and usable for building product. |
| FR2716392B1 (en) * | 1994-02-22 | 1996-04-12 | Commissariat Energie Atomique | Extraction of heavy metals contained in fly ash and smoke purification residues from an incineration oven. |
| JP3178252B2 (en) * | 1994-07-19 | 2001-06-18 | 三菱マテリアル株式会社 | Metal recovery from fly ash |
| ZA963234B (en) * | 1995-05-02 | 1996-07-29 | Holderbank Financ Glarus | Process for the production of hydraulic binders and/or alloys such as e g ferrochromium of ferrovanadium |
-
1996
- 1996-02-08 AT AT0023396A patent/AT405191B/en not_active IP Right Cessation
-
1997
- 1997-01-15 HR HRA233/96 patent/HRP970030B1/en not_active IP Right Cessation
- 1997-02-05 EP EP97901474A patent/EP0820532A1/en not_active Withdrawn
- 1997-02-05 CZ CZ973058A patent/CZ305897A3/en unknown
- 1997-02-05 WO PCT/AT1997/000021 patent/WO1997029214A1/en not_active Application Discontinuation
- 1997-02-05 HU HU9901450A patent/HUP9901450A2/en unknown
- 1997-02-05 SK SK1324-97A patent/SK132497A3/en unknown
- 1997-02-05 CA CA002216714A patent/CA2216714A1/en not_active Abandoned
- 1997-02-07 ZA ZA9701032A patent/ZA971032B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| HRP970030B1 (en) | 2000-08-31 |
| MX9707650A (en) | 1998-08-30 |
| CZ305897A3 (en) | 1999-01-13 |
| SK132497A3 (en) | 1998-04-08 |
| HUP9901450A2 (en) | 1999-08-30 |
| ZA971032B (en) | 1997-09-03 |
| EP0820532A1 (en) | 1998-01-28 |
| HRP970030A2 (en) | 1998-04-30 |
| AT405191B (en) | 1999-06-25 |
| ATA23396A (en) | 1998-10-15 |
| WO1997029214A1 (en) | 1997-08-14 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| FZDE | Discontinued |