EP2678406A1 - Procédé pour traiter du matériau cathodique usagé contenant du carbone - Google Patents

Procédé pour traiter du matériau cathodique usagé contenant du carbone

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Publication number
EP2678406A1
EP2678406A1 EP12706807.0A EP12706807A EP2678406A1 EP 2678406 A1 EP2678406 A1 EP 2678406A1 EP 12706807 A EP12706807 A EP 12706807A EP 2678406 A1 EP2678406 A1 EP 2678406A1
Authority
EP
European Patent Office
Prior art keywords
shaft furnace
carbon
longitudinal section
cathode material
shaft
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.)
Granted
Application number
EP12706807.0A
Other languages
German (de)
English (en)
Other versions
EP2678406B1 (fr
Inventor
Alfred Edlinger
Johann Daimer
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.)
SGL Carbon SE
Original Assignee
SGL Carbon SE
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Filing date
Publication date
Application filed by SGL Carbon SE filed Critical SGL Carbon SE
Publication of EP2678406A1 publication Critical patent/EP2678406A1/fr
Application granted granted Critical
Publication of EP2678406B1 publication Critical patent/EP2678406B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/06—Continuous processes
    • C10J3/18—Continuous processes using electricity
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/20—Apparatus; Plants
    • C10J3/22—Arrangements or dispositions of valves or flues
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/20—Apparatus; Plants
    • C10J3/22—Arrangements or dispositions of valves or flues
    • C10J3/24—Arrangements or dispositions of valves or flues to permit flow of gases or vapours other than upwardly through the fuel bed
    • C10J3/26—Arrangements or dispositions of valves or flues to permit flow of gases or vapours other than upwardly through the fuel bed downwardly
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/20—Apparatus; Plants
    • C10J3/34—Grates; Mechanical ash-removing devices
    • C10J3/40—Movable grates
    • C10J3/42—Rotary grates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/57—Gasification using molten salts or metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/103—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkali- or earth-alkali- or NH4 salts or inorganic acids derived from sulfur
    • 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
    • F23G5/0276—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage using direct heating
    • 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
    • F23G5/08—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating
    • F23G5/10—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating electric
    • 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
    • F23G5/08—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating
    • F23G5/14—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating including secondary combustion
    • F23G5/16—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating including secondary combustion in a separate combustion chamber
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/003—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals for used articles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2200/00—Details of gasification apparatus
    • C10J2200/15—Details of feeding means
    • C10J2200/156—Sluices, e.g. mechanical sluices for preventing escape of gas through the feed inlet
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C10J2300/0976—Water as steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/12—Heating the gasifier
    • C10J2300/123—Heating the gasifier by electromagnetic waves, e.g. microwaves
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2201/00—Pretreatment
    • F23G2201/30—Pyrolysing
    • F23G2201/301—Treating pyrogases
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2201/00—Pretreatment
    • F23G2201/30—Pyrolysing
    • F23G2201/303—Burning pyrogases
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2201/00—Pretreatment
    • F23G2201/70—Blending
    • F23G2201/701—Blending with additives
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2202/00—Combustion
    • F23G2202/20—Combustion to temperatures melting waste
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2204/00—Supplementary heating arrangements
    • F23G2204/20—Supplementary heating arrangements using electric energy
    • F23G2204/204—Induction
    • 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
    • F23G2900/50001—Combination of two or more furnaces

Definitions

  • the invention relates to a method for reprocessing spent carbonaceous cathode material, in particular spent cathode tubs from aluminum production, in which the cathode material fed to a shaft furnace and in the shaft furnace for the gasification of carbon heat treatment at a temperature above the ignition temperature of the carbon and above Evaporating temperature of toxins contained in the spent cathode material is subjected.
  • the cathode material fed to a shaft furnace and in the shaft furnace for the gasification of carbon heat treatment at a temperature above the ignition temperature of the carbon and above Evaporating temperature of toxins contained in the spent cathode material is subjected.
  • the electrolysis cell usually consists of a steel tub, which is lined with carbon material (graphite / anthracite) and a refractory material, such as fireclay.
  • the carbon lining serves as a cathode in the electrolysis and is therefore referred to as a cathode trough in the sequence.
  • Used cathode pans also called Spent Potliners, are produced in large quantities in aluminum production according to the Hall-Heroult process and have always posed a problem in terms of disposal due to their high contents of toxic substances.
  • the toxic substances are, in particular, cyanide, which is formed from the carbon of the cathode pans and the nitrogen of the air and various metal fluorides, such as sodium and aluminum fluoride, which are formed from the metal species contained in the bauxite together with the fluoride of the cryolite used in the Hall-Heroult process.
  • cyanide which is formed from the carbon of the cathode pans and the nitrogen of the air
  • various metal fluorides such as sodium and aluminum fluoride, which are formed from the metal species contained in the bauxite together with the fluoride of the cryolite used in the Hall-Heroult process.
  • the method mentioned above is further developed in accordance with the invention in that the reaction gases are conducted in a first longitudinal section of the shaft furnace in co-current with the carbon and in a second longitudinal section of the shaft furnace in countercurrent to the carbon and in that the reaction gases from a region of Shaft furnace with an enlarged cross-section, in particular an enlarged diameter, between the mentioned stripped th longitudinal sections and preferably subjected to a post-treatment.
  • reaction gases are withdrawn in a middle region along the longitudinal axis of the shaft furnace (central gas withdrawal)
  • alkaline cycles are interrupted and the reaction gases which contain the mentioned toxicants in the form of sodium fluoride (NaF), aluminum fluoride (A1F 3 ), hydrofluoric acid (HF ), Nitrogen (N 2 ) and optionally further alkali metal and alkaline earth metal fluorides in addition to synthesis gas (CO + H 2 ), can be fed to a further workup.
  • the process is autothermic due to the high C content when the carbon has reached the ignition temperature and sufficient oxygen is available for gasification.
  • it is provided according to a preferred embodiment to heat the furnace to heat the carbon of the spent cathode material to the reaction temperature.
  • this heating can be carried out in all manners known to the person skilled in the art.
  • the energy for the thermal treatment can be introduced, for example, by electrical induction into the carbon to be worked up.
  • induction coils may be arranged around the circumference of the shaft furnace in the region of the discharge end of the shaft furnace, with which an induction field is built up, to which the introduced carbon of the used cathode material couples and thereby heats up.
  • the heating can also be effected by fossil firing, for example by placing in the shaft furnace, preferably in the first longitudinal section of the shaft furnace and in particular in the upper region of the first longitudinal section.
  • a combustion shaft is arranged through which in the shaft furnace a fuel, such as natural gas, petroleum, coal dust, produced from spent cathode tubs dust or the like, optionally in mixture with a Oxidati- onsgas, such as oxygen or air, is introduced.
  • a feed line opening into the first longitudinal section of the shaft furnace preferably into the upper section of the first longitudinal section of the shaft furnace, via which fuel is optionally supplied to the shaft furnace in admixture with oxidizing gas.
  • one or more lances preferably extending substantially in the direction of the longitudinal extension of the shaft furnace, through which the Shaft furnace fuel and oxidizing gas, separately or mixed with each other, are supplied.
  • the carbon of the spent carbonaceous cathode material may also be brought to reaction temperature by charging a portion of already glowing coke or graphite to the spent cathode material introduced into the shaft furnace or the spent cathode material upon its introduction in the shaft furnace or before a subset of already glowing coke or graphite is added.
  • the present invention is not limited to either absolute or relative dimensions of the individual longitudinal sections.
  • the length of the first Longitudinal section 40 to 80% preferably 50 to 70% and particularly preferably 60 to 70% of the total length of the shaft furnace.
  • the length of the second longitudinal section is preferably 20 to 60%, more preferably 30 to 50% and most preferably 30 to 40% of the total length of the shaft furnace.
  • the shaft furnace or its longitudinal sections can in this case have a circular cross-section.
  • a rectangular section embodiment is preferred. This is particularly preferred because of the skin effect, which leads to the fact that the penetration depth of the electrodynamic field is limited.
  • oxygen is injected in the first and / or second longitudinal section of the shaft furnace.
  • oxidation of the carbon to CO 2 takes place, which is, however, reduced to CO in the carbon bed in the shaft furnace after the Boudouard equilibrium.
  • calorific value-containing carbon monoxide can be obtained.
  • the cyanide (CN.sup. + Compound) contained in the consumed cathode material is oxidized under the prevailing reaction conditions. also converted to carbon monoxide and nitrogen and thus completely destroyed.
  • the process according to the invention is preferably further developed such that water or water vapor is injected in the first and / or second longitudinal section of the shaft furnace.
  • Fluorides and alkali compounds, which are present, for example, as sodium fluoride, are volatilized in the presence of water or steam according to the following reaction scheme and are thereby converted into the gas phase:
  • the elemental sodium is gaseous and is removed via the central gas outlet, before forming in the shaft furnace by condensation on colder, the furnace down through the trimming material.
  • HF hydrofluoric acid
  • sodium fluoride is formed again and can be deposited in the subsequent exhaust gas treatment.
  • Another way to remove fluorides is their reaction with silica according to:
  • the method according to the invention is carried out in such a way that oxygen and water or water vapor are blown into the shaft furnace with the aid of lances.
  • oxygen and water or water vapor are injected only via nozzles that open at the wall of the shaft furnace, only the edge zones of the shaft furnace or the carbon bed are fed in the shaft furnace, while the inner region of the cross section of Carbon bed remains undersupplied and in these areas, the reaction rate is therefore very low or an autothermal procedure may not even be achieved.
  • the substances mentioned can be introduced, for example, precisely at the points which lie in the region of the induction heating, whereby reaction spaces are generated which are sufficiently hot that the process in the sequence along the entire shaft furnace runs autothermally.
  • powdered or dusty spent carbonaceous cathode material, in particular cathode pans can be blown.
  • the process may preferably be developed such that non-gasified carbon is dissolved in an iron bath.
  • the iron bath can be heated, for example, inductively.
  • an iron bath ensures an outstanding solution kinetics for carbon and can be easily regenerated by blowing in oxygen, so-called fresh. As this refining is an exothermic reaction, the heat balance of the process is improved.
  • the blowing in of the oxygen can also be carried out continuously in order to keep the iron bath constant C-undersaturated.
  • the spent carbonaceous cathode material at its introduction into the shaft furnace or before slagging refractory material, ie as stated above, in particular aluminum, silicon and magnesium oxide, which in the consumed carbonaceous cathode material are contained as residues of Feuerfestausmautation to add an additive.
  • elemental calcium and all calcium-containing compounds which are also referred to below as the Ca-carrier
  • elemental magnesium and all magnesium-containing compounds which are also referred to below as Mg support in question.
  • suitable Ca carriers are CaO and CaC 3 , which are available, for example, in the form of steelworks slag, limestone or burnt lime and are preferably added to the process in a coarse-grained manner in order to keep the carbon bed or column thoroughly permeable.
  • suitable Mg supports are MgO and MgC 3 , which are preferably also added to the process in a coarse-grained manner in order to keep the carbon bed or column well passable.
  • the additive ie preferably Ca carrier or Mg carrier
  • the aluminum, silicon and magnesium oxides of the refractory material high quality slags namely in the case of the addition of Ca carrier high-quality calcium aluminate slags can be obtained which have excellent hydraulic properties and can therefore be used advantageously in the cement industry for the production of hydraulic binders.
  • high-grade magnesium aluminate slags or Spinel slags obtained, which can be used for example as Feuerbetone.
  • a calcium aluminate slag having an Al 2 O 3 content of more than 70% in the shaft furnace to 90 wt .-%, preferably 75 to 85 wt .-% and particularly preferably about 80 wt .-% is generated. Due to the high melting point of the slag, a sintering phase is produced.
  • these calcium aluminates are particularly suitable for use in the production of rapid cements, for increasing the early strength of composite cements or in the form of sulphate-stimulated slag cements or gypsum slag cements.
  • the use of these calcium aluminates in cements is particularly advantageous because it significantly reduces the clinker factor in cement production, ie the proportion of Portland cement clinker per ton of cement. In terms of climate policy, this is advantageous because the production of 1 ton Portland cement clinker produces about 1 tonne of carbon dioxide.
  • the calcium aluminates thus produced can be used for the production of refractory materials and for the production of cke, ie a mixture of CaF 2 , Al 2 O 3 and CaO, which in turn is used to obtain highly resilient steel components, can be used.
  • the calcium aluminates produced in this way can also be used in the area of raw iron sulphurization or secondary metallurgy, which is advantageous, inter alia, because this avoids the problematic use of fluorspar.
  • the process according to the invention preferably uses spent carbonaceous cathode material having an aluminum oxide content of from 10 to 45% and particularly preferably from 15 to 30%.
  • the process may also be carried out so that the carbon of the cathode material is completely gasified and the remaining calcine is discharged.
  • an additive more preferably a Ca support and / or Mg support, may be added to the spent carbonaceous cathode material when it is introduced into the shaft furnace or before, but need not. If no additive is added, a dry discharge of the virtually carbon-free takes place Calcinate consisting of aluminum and silicon oxide, which can also be used in the cement industry. It has been observed that incomplete calcine may break down into carbonaceous powder.
  • the powder form Due to the powder form, however, this is then no longer permeable to gas and the corresponding shaft furnace part no longer has gas permeability.
  • the following aftertreatment options are conceivable. There may be a post-treatment on the iron bath as described above. Alternatively, the powder may be treated for decarburization by means of steam, whereby a simultaneous cooling is achieved due to the endothermic heterogeneous water gas reaction.
  • the process is preferably carried out with strongly acidic slag.
  • a strongly acidic slag wherein the acidic component can be formed for example by silica and / or alumina
  • the new formation of hydrofluoric acid is carried out according to the following reaction equation:
  • the process is therefore preferably developed in such a way that the basicity in the shaft furnace is adjusted by the addition of basic or acidic additives, in particular CaO or SiO 2 .
  • basic or acidic additives in particular CaO or SiO 2 .
  • a particularly preferred procedure provides that the addition of basic and acidic additives is carried out alternately. In this way, sodium fluoride and hydrofluoric acid are alternately obtained.
  • the hydrofluoric acid can be reacted with alumina ( ⁇ 1 2 0 3 ) to aluminum fluoride (A1F 3 ) and water, wherein the aluminum fluoride can be further processed with the obtained in the basic procedure sodium fluoride (NaF) to cryolite (Na 3 AlF 6 ), which in turn can be used in aluminum production by the Hall-Heroult process.
  • the process is carried out such that the reaction gases are withdrawn at a temperature of 800 ° C to 1200 ° C, in particular 900 ° C to 1100 ° C, in particular 1000 ° C and fed to the aftertreatment, whereby a condensation of the reaction gases or toxins is prevented in the piping systems and a controlled exhaust gas treatment can be ensured.
  • the maximum temperature in the hearth of the furnace is preferably 1200 to 1700 ° C, more preferably 1400 to 1700 ° C and most preferably 1500 to 1600 ° C. This maximum temperature is reduced to a maximum of 1200 ° C by endothermic reactions and by heat losses up to the middle gas outlet.
  • reaction gas withdrawn from the shaft furnace which contains not only carbon monoxide, carbon dioxide, hydrogen, possibly water and dust discharged from the reactor, but also volatilized compounds, in particular hydrofluoric acid, sodium fluoride, aluminum fluoride and others, in a cooled and preferably isothermally operated and particles, which are, for example, made of aluminum oxide, sodium fluoride, aluminum fluoride, calcium carbonate, aluminum hydroxide or the like, containing fluidized bed reactor is passed.
  • the temperature of the fluidized bed can be easily adjusted to a suitable value by, for example, a water-driven heat exchanger or a water evaporator, wherein in the shaft furnace due to the strong turbulence of the fluidized bed, a uniform temperature of for example about 1,000 ° C, about 1,100 ° C or about 1,200 ° C is guaranteed.
  • the fluidized aluminum oxide particles undergo rapid cooling, condensation and, if appropriate, reaction of the volatilized compounds of the exhaust gas, as a result of which cryolite or similar compounds form on the aluminum oxide particles.
  • purified exhaust gas is withdrawn from the fluidized bed reactor, wherein from the exhaust gas in a reactor downstream cyclone or a further dry absorption of alumina or alumina in countercurrent at low temperature any remaining, loaded with reaction products alumina particles are separated.
  • silicon fluoride (SiF 4 ) can be separated from the exhaust gas obtained in this way.
  • this treatment is wastewater-free, this has the advantage of requiring only relatively small devices.
  • a further advantage of this aftertreatment is that it produces heat which is used to heat the process steam required for the shaft furnace can.
  • the product formed from the particles and the exhaust gas can be used in aluminum production.
  • FIG. 1 shows a schematic view of a shaft furnace suitable for carrying out the method according to the invention in accordance with a first exemplary embodiment
  • FIG. 2 shows a schematic view of a shaft suitable for carrying out the method according to the invention
  • FIG. 3 shows a schematic view of a shaft furnace suitable for carrying out the method according to the invention with an iron bath according to a further exemplary embodiment
  • FIG. 4 shows a schematic view of an overall system suitable for carrying out the method according to the invention
  • 6 shows a schematic view of a shaft furnace suitable for carrying out the method according to the invention, according to a still further exemplary embodiment
  • FIG. 7 shows a schematic view of the upper section of a fossil heating shaft furnace suitable for carrying out the method according to the invention, according to a further exemplary embodiment
  • Fig. 8 is a schematic view of the upper portion of a suitable for carrying out the method according to the invention fossil furnace shaft furnace according to yet another embodiment and
  • FIG. 9 shows a schematic view of the upper section of a fossil heating shaft furnace suitable for carrying out the method according to the invention in accordance with a further exemplary embodiment.
  • Fig. 1, 1 denotes a shaft furnace, which in the implementation of the method according to the invention at the position 2 spent cathode tubs, which are also known as Spent Potliner, abandoned in broken form.
  • the carbon pieces are spent by means of a rotary valve 3 in the shaft 4 of the shaft furnace 1, which can already be introduced at the height of the rotary valve 3 via a loop 5 oxygen.
  • Indicated at 6 are induction loops which introduce an induction field in the cross section of the shaft furnace 1, so that the carbon of the spent cathode troughs coupled and heated to an ignition temperature of, for example, 600 ° C to 800 ° C.
  • the shaft In area 7 of the shaft furnace points the shaft has an enlarged diameter compared to the first axial longitudinal section 8 and the second axial longitudinal section 9, so that the reaction gases can be deducted from an annular space 10 as indicated by the arrow 11.
  • the reaction gases contain carbon monoxide, carbon dioxide, sodium fluoride, sodium, nitrogen, hydrofluoric acid, hydrogen and optionally beryllium fluoride as main components. Because the carbon of the spent cathode walls is consumed by the gasification reaction, the carbon column 12 present in the shaft furnace, which is in fact formed by the carbon of the used cathode material, decreases in the direction of the arrow 13.
  • the reaction gases in the first longitudinal section 8 are guided in cocurrent with the carbon and in the second longitudinal section 9 of the shaft furnace in countercurrent to the carbon.
  • the countercurrent in the kinetic imbalance is carried out for the Boudouard reaction, whereby the carbon dioxide content in the exhaust gas is maximized, so that only a short countercurrent bed is necessary.
  • nozzles 14 are mounted in the second longitudinal section 9 of the shaft furnace over which also oxygen and / or water or water vapor can be blown.
  • Other nozzles with the same functionality are located at position 15.
  • With 16 is another rotary valve designated over which calcine can be discharged.
  • the lower portion 17 is to be understood as a cooling section, as above the nozzles 15 especially water in liquid form and possibly to be introduced as steam or wet steam.
  • FIG. 1 An alternative to the process control shown in FIG. 1 is shown in FIG. While a complete gasification of the carbon is to take place in FIG. 1, non-gasified carbon can be dissolved in an iron bath 18 in the process of FIG. Otherwise, the shaft furnace is constructed substantially the same and in particular also has a region 7 with an enlarged diameter, from which the exhaust gases at position 11 can be withdrawn.
  • the iron bath 18 is saturated with carbon, oxygen is blown into the iron bath via the lance 19, whereby at the position 20 pure carbon monoxide escapes, which can subsequently be thermally utilized.
  • fluoride-free slag can be tapped and sent for use in the cement industry.
  • the iron bath 18 is arranged in the shaft furnace 1, wherein the Schlackenabstich the fluoride-free slag takes place at the position 22.
  • area 23 of the shaft furnace there is a melting zone in which iron recarburization occurs.
  • the reaction gas is sucked out of an annular space 10 from the region 7 with an enlarged diameter at the position 11.
  • a quench 24, a caustic soda absorber 25 and an aerosol demister 26 are part of the system for reprocessing the spent fuel.
  • th cathode wells is.
  • the shaft furnace 1 has the features already described, in which case the discharge is not via a rotary valve, but via a rotating cone 27, which is hollow and can be charged via the line 28, for example with steam, so that the cone like a lance Releases water vapor into the interior of the carbon bed.
  • the withdrawal of the reaction gases is again at the position 11, wherein the gases are passed in a first step in a gas cooler 29 before they get into the quenches 24. There they are mixed with water as aerosol and relaxed. Sodium fluoride can be withdrawn at position 30.
  • the neutralization of the hydrofluoric acid is carried out by sodium hydroxide solution.
  • beryllium fluoride can be withdrawn at position 31.
  • the aerosol demister 26 residual sodium fluoride and beryllium are separated from the gas stream, which is a pure synthesis gas consisting of carbon monoxide and hydrogen in the sequence.
  • a lance 33 opens, which consists of an inner tube 34 and an outer tube 35.
  • the two tubes 34 and 35 can be displaced or telescoped against the shaft furnace and against one another, wherein oxygen is introduced through the inner tube and water or water vapor is introduced into the shaft 4 of the shaft furnace 1 through the outer tube.
  • the lance 33 can be moved against the shaft, it is possible to mechanically manipulate the bed 12 in the shaft 4 of the shaft furnace 1, so that mechanical bridges are broken and the discharge in the region 36 is ensured.
  • a pivotable flap 37 is attached. brought, on which the calcinate comes to rest with the natural angle of repose.
  • FIG. 5 further shows that the shaft furnace 1 can generally also have a rectangular cross section instead of a circular cross section. This is illustrated in FIG. 5 by the wall 43 drawn in dashed lines, wherein both the first longitudinal section and the second longitudinal section can have a rectangular cross-section at least in sections. As favorable here a clear width of 600 to 800 mm has been found.
  • the second longitudinal section of the shaft furnace has the wall 44 which is shown on the right in FIG. 5 and widens toward the exhaust opening.
  • FIG. 6 shows an alternative embodiment in which the calcinate is conveyed by means of a vibrating bottom 40 in the direction of a conveyor screw 41 in order in this way likewise to be fed to a discharge lock 42.
  • the Rüttelêt 40 in this case has a passage opening for a lance 33.
  • a shaft furnace 1 in which the heating to the starting material, ie the carbon of the consumed cathode material to heat to the reaction temperature, in contrast to the embodiments shown in FIGS. 1 to 6 is not carried out by an induction heating induction heating, but by fos- silse firing.
  • a combustion shaft 45 is provided in the first, upper longitudinal section 8 of the shaft furnace 1, via which the shaft furnace 1 during its operation fuel, such as natural gas, is supplied.
  • the mixture of broken spent cathode troughs and calcium oxide consequently passes via the double-bell lock 47 from the application area 2 into the annular shaft 46, in which this mixture impinges on the already heated carbon charge.
  • the lower portion of the shaft furnace not shown in Fig. 7 may be formed as in any of the embodiments shown in Figs.
  • the shaft furnace 1 of this embodiment is preferably operated so that at the gas outlet 11 reaction gas withdrawn at a temperature of about 1200 ° C. becomes.
  • the shaft furnace 1 can also be provided with a mixture of fuel and oxidizing gas through the combustion shaft 45 and water or water vapor optionally mixed with oxygen or air via the loop 5.
  • Fig. 8 there is shown an alternative embodiment to that shown in Fig. 7, in which the shaft furnace 1 is also fired fossil.
  • a fuel supply line 48 is provided in the shaft furnace 1 of FIG. 8 for introducing the fuel into the upper region of the first, upper longitudinal section via which the shaft furnace 1 receives fuel, in particular natural gas. or a mixture of fuel and oxidizing gas, such as oxygen or air, is supplied. If the shaft furnace 1 via the fuel supply line 48 only fuel is supplied to the shaft furnace 1 via the ring line 5, an oxidizing gas is supplied.
  • a mixture of fuel and oxidizing gas is supplied to the shaft furnace 1 via the ring line 5 water or water vapor may optionally be supplied in admixture with oxygen or air.
  • the feeding of the shaft furnace 1 takes place via the feed area 2, which for the purpose of metering can optionally have a rotary feeder as configured in FIG. 1.
  • the lower portion of the shaft furnace not shown in FIG. 8 may be formed as in any of the embodiments shown in FIGS.
  • Fig. 9 there is shown an alternative embodiment to that shown in Figs. 7 and 8, in which the shaft furnace 1 is also fired fossil. Instead of the combustion shaft 45 shown in FIG. 7 or the fuel supply line 48 shown in FIG.
  • lances 19, 19 'extending in the longitudinal direction of the shaft furnace 1 are provided in the shaft furnace 1 of FIG. 9 for introducing the fuel into its upper region. via which the shaft furnace 1 oxygen is supplied, and lances 49, 49 ', via which the shaft furnace 1 fuel is supplied, provided. These lances are arranged in uniform concentric about the longitudinal axis of the shaft furnace 1. Again, a ring line 5 is provided, via which the shaft furnace 1 oxygen or air and / or water or water vapor can be supplied.
  • the lower portion of the shaft furnace not shown in FIG. 9 may be formed as in any of the embodiments shown in FIGS.

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Abstract

L'invention concerne un procédé pour traiter du matériau cathodique usagé contenant du carbone, en particulier des cuves cathodiques pour la production d'aluminium, selon lequel le matériau cathodique est chargé dans un four à cuve et est soumis dans le four à cuve à un traitement thermique à une température supérieure à la température d'inflammation du carbone et supérieure à la température d'évaporation des gaz nocifs contenus dans le matériau cathodique usagé pour la gazéification du carbone. Les gaz de réaction sont guidés dans une première partie longitudinale du four à cuve dans le même sens du courant que le carbone et dans une deuxième partie longitudinale du four à cuve à contre-courant du carbone, les gaz de réaction étant soutirés d'une région du four à cuve ayant une section transversale agrandie entre lesdites parties longitudinales et étant soumis de préférence à un post-traitement.
EP12706807.0A 2011-02-23 2012-02-22 Procédé pour traiter du matériau cathodique usagé contenant du carbone Not-in-force EP2678406B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA245/2011A AT510686B1 (de) 2011-02-23 2011-02-23 Verfahren zum aufarbeiten von verbrauchtem kohlenstoffhaltigen kathodenmaterial
PCT/EP2012/053006 WO2012113826A1 (fr) 2011-02-23 2012-02-22 Procédé pour traiter du matériau cathodique usagé contenant du carbone

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EP2678406A1 true EP2678406A1 (fr) 2014-01-01
EP2678406B1 EP2678406B1 (fr) 2015-04-15

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US (1) US9199109B2 (fr)
EP (1) EP2678406B1 (fr)
CN (1) CN103415596B (fr)
AT (1) AT510686B1 (fr)
AU (1) AU2012219652B2 (fr)
BR (1) BR112013021512A2 (fr)
CA (1) CA2827720C (fr)
ES (1) ES2537286T3 (fr)
MY (1) MY163997A (fr)
RU (1) RU2556660C2 (fr)
UA (1) UA105613C2 (fr)
WO (1) WO2012113826A1 (fr)
ZA (1) ZA201306297B (fr)

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WO2014026138A1 (fr) * 2012-08-09 2014-02-13 Alcoa Inc. Brasque usée à teneur élevée en carbone et procédés d'alimentation d'un four avec celle-ci
DE102013218521A1 (de) 2013-09-16 2015-03-19 Sgl Carbon Se Schachtofen und Verfahren zum Aufarbeiten von einem Fluor enthaltenden Abfallprodukt
DE102013022099A1 (de) 2013-12-21 2015-06-25 ingitec Engineering GmbH Recycling von Spent Pot Lining
KR20210114939A (ko) * 2018-11-28 2021-09-24 케이비아이 인베스트 & 매니지먼즈 에이쥐 공급 물질의 가스화 및 / 또는 용해를 위한 반응기 및 프로세스
CN111892963B (zh) * 2020-08-17 2022-04-05 山东魏桥铝电有限公司 一种电解铝废旧阴极炭块气化及再燃脱硝方法
CN113154412B (zh) * 2021-04-17 2024-08-16 浙江宜可欧环保科技有限公司 热解脱附气的资源化处理方法
CN113488779A (zh) * 2021-06-29 2021-10-08 电子科技大学 一种热塑型填料吸波锥体结构及其制作方法
CN113714515B (zh) * 2021-09-16 2024-02-23 武汉联影医疗科技有限公司 一种阴极材料及其制备方法、装置
EP4186963A1 (fr) * 2021-11-25 2023-05-31 Speira GmbH Matière à base de brasque usée stable au stockage, son procédé de fabrication, ainsi que son utilisation en tant que combustible
CN114231318B (zh) * 2021-12-17 2024-03-01 自贡市南方锅炉机械配套设备制造有限公司 一种环保垃圾气化设备
DE102023113080A1 (de) 2023-05-17 2024-11-21 FURNACE DESIGN GmbH Vorrichtung zum Erhitzen von Gasen

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US20130338421A1 (en) 2013-12-19
WO2012113826A1 (fr) 2012-08-30
RU2013142926A (ru) 2015-04-10
CN103415596A (zh) 2013-11-27
UA105613C2 (uk) 2014-05-26
AT510686B1 (de) 2012-06-15
AU2012219652A1 (en) 2013-05-02
EP2678406B1 (fr) 2015-04-15
AU2012219652B2 (en) 2015-07-16
CN103415596B (zh) 2016-12-07
AT510686A4 (de) 2012-06-15
MY163997A (en) 2017-11-15
RU2556660C2 (ru) 2015-07-10
ES2537286T3 (es) 2015-06-05
CA2827720C (fr) 2017-07-18
US9199109B2 (en) 2015-12-01
ZA201306297B (en) 2014-04-30
CA2827720A1 (fr) 2012-08-30
BR112013021512A2 (pt) 2019-09-24

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