EP4186963A1 - Matière à base de brasque usée stable au stockage, son procédé de fabrication, ainsi que son utilisation en tant que combustible - Google Patents

Matière à base de brasque usée stable au stockage, son procédé de fabrication, ainsi que son utilisation en tant que combustible Download PDF

Info

Publication number
EP4186963A1
EP4186963A1 EP21210576.1A EP21210576A EP4186963A1 EP 4186963 A1 EP4186963 A1 EP 4186963A1 EP 21210576 A EP21210576 A EP 21210576A EP 4186963 A1 EP4186963 A1 EP 4186963A1
Authority
EP
European Patent Office
Prior art keywords
cathode
breakout
wax
hydrophobic binder
material according
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.)
Pending
Application number
EP21210576.1A
Other languages
German (de)
English (en)
Inventor
Ralf Lemke
Olaf Güssgen
Kathrin Eckhard
Joachim Höfler
Andreas Beermann
Thorsten Kensy
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.)
Speira GmbH
Original Assignee
Speira GmbH
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 Speira GmbH filed Critical Speira GmbH
Priority to EP21210576.1A priority Critical patent/EP4186963A1/fr
Priority to PCT/EP2022/083258 priority patent/WO2023094584A1/fr
Priority to CN202280077929.7A priority patent/CN118302506A/zh
Priority to AU2022397819A priority patent/AU2022397819A1/en
Priority to CA3239118A priority patent/CA3239118A1/fr
Publication of EP4186963A1 publication Critical patent/EP4186963A1/fr
Priority to US18/667,403 priority patent/US20240301313A1/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • C10L5/48—Solid fuels essentially based on materials of non-mineral origin on industrial residues and waste materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
    • C10L5/10—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders
    • C10L5/14—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with organic binders
    • C10L5/146—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with organic binders with wax, e.g. paraffin wax
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/10—Treating solid fuels to improve their combustion by using additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0453—Petroleum or natural waxes, e.g. paraffin waxes, asphaltenes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0484—Vegetable or animal oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/14—Function and purpose of a components of a fuel or the composition as a whole for improving storage or transport of the fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/06—Heat exchange, direct or indirect
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/24—Mixing, stirring of fuel components
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/28—Cutting, disintegrating, shredding or grinding
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/546—Sieving for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/34—Other details of the shaped fuels, e.g. briquettes
    • C10L5/36—Shape
    • C10L5/361—Briquettes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/34—Other details of the shaped fuels, e.g. briquettes
    • C10L5/36—Shape
    • C10L5/363—Pellets or granulates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium

Definitions

  • the invention relates to a cathodic material, a process for its production and its use as a fuel, preferably in power stations and in the production of mineral wool, cement and steel.
  • Aluminum is usually produced by fused-salt electrolysis in aluminum electrolytic cells using the Hall-Heroult process. During the electrolysis of the molten mixture of alumina and cryolite, the aluminum formed is deposited on the cathode and, on the anode, oxygen reacts with the graphite of the anode to form carbon dioxide and carbon monoxide. Over time, the graphite anodes will wear out and need to be replaced.
  • the cathode lining which also consists primarily of graphite, is inert to aluminum.
  • sodium from the molten bath is absorbed by the cathode lining and forms intercalation compounds that change the wetting behavior of the cathode lining with respect to the electrolyte.
  • the molten cryolite and alumina salts can then more easily penetrate through pores and cracks into the cathode lining and over time completely impregnate it, thereby degrading the electrolytic cell's productivity and energy consumption.
  • the content of iron and silicon impurities in the aluminum is increased.
  • the average service life of the cathode lining in industrial aluminum electrolytic cells is usually between 4 and 7 years. Actual lifetime can also be significantly shorter if premature cathode liner failure occurs, usually caused by cracks in the cathode liner.
  • the cathode liner is broken open and removed mechanically, for example using jackhammers.
  • the resulting cathode spall also known as "spent pot lining (SPL)"
  • SPL super pot lining
  • the first cut which consists of the cathode lining graphite
  • the second cut which is a mixture of the cathode lining graphite and the refractory lining.
  • the cathodic breakout consists of about 55% of the first cut and 45% of the second cut.
  • the first cut cathode breakout is predominantly graphite with low volatiles and sulfur content.
  • toxic compounds such as cyanides, for example in the form of sodium cyanide, and fluoride compounds accumulate during aluminum electrolysis on or in the cathode lining. These toxic compounds have a high reactivity with water and/or air, in particular oxygen, which can lead to the development of heat, toxic gases and inflammation.
  • Cathode flare is therefore classified as hazardous waste and dangerous goods in most countries, for example under the European Agreement concerning the International Carriage of Dangerous Goods by Road (ADR).
  • cathodic flare is identified in the transport documents as UN3170 WASTE, ALUMINUM PRODUCTION BY-PRODUCTS, 4.3, III, (E) and is classified as a Dangerous Good of Class 4.3: "Substances which, in contact with water, emit flammable gases".
  • cathode slag has a thermally interesting calorific value, so that the use of cathode skeleton as fuel is desirable as a possible disposal route.
  • cathodic debris classified as dangerous goods is limited by the complex transport, storage and processability.
  • usefulness of the cathode spall as a fuel, as well as its disposal costs is highly dependent on the size of the cathodic spall fragments.
  • the WO 2014/026138 A1 describes a cathodic eruption containing at least 65% by weight carbon content and its use as a fuel.
  • the high carbon content is produced by using only the first cut of the cathode breakout and optionally adding thereto a carbon-enriching compound, the carbon-enriching compound being selected from compatible metallurgical residues such as by-products of graphite anode or graphite cathode production.
  • Such by-products are WO 2014/026138 A1 unspecified, but could be, for example, dust, fragments or offcuts from production scrap.
  • the carbon-enriched cathode slag generated in this way has a higher calorific value, it is still a hazardous material due to the cyanides and fluorides contained in the cathode sliver, which are highly reactive with water and/or atmospheric oxygen.
  • the WO 88/06572 A1 describes a process for the production of mineral wool in which, inter alia, briquettes consisting of a mixture of cathode spoil and bituminous coke and coke oven pitch are used as part of the fuel charge of the mineral wool cupola furnace. This is intended to reduce unwanted silicon deposits in the furnace that occur during the manufacture of the mineral wool.
  • the briquette should preferably contain about 40% hard coal coke, 0.45% cathodic debris and 15% coke pitch.
  • a disadvantage of these briquettes is that they contain only extremely small amounts of cathode debris and therefore only small portions of the cathode debris can be used as fuel and disposed of.
  • the coke oven pitch used as a binder is technically difficult to handle due to its high stickiness, the processing window at high temperatures and the partly carcinogenic ingredients such as polycyclic aromatic hydrocarbons.
  • the object of the invention was to provide a cathode breakout material, which allows for safe storage and safe transport of smaller-grain fractions and dusts of the Guaranteed cathode eruption and does not have the disadvantages mentioned in the prior art.
  • Another object of the invention was to provide a simple method for producing such a cathode blast material.
  • cathodic material containing cathodic material, in particular from aluminum electrolytic cells, and at least one hydrophobic binder, the hydrophobic binder being selected from wax, a waxy compound or mixtures thereof.
  • the subject matter of the invention is also a method for the production of a cathode spoilage material and the use of the cathode spoilage material according to the invention as a fuel.
  • a cathode blast material which has no appreciable reactivity towards water and/or atmospheric oxygen, so that its storage and transport stability is ensured.
  • the cathode eruption is rendered inert to such a complete extent by the addition of the hydrophobic binders provided according to the invention that it is no longer considered hazardous waste to be transported.
  • the cathode breakout material according to the invention no longer develops any flammable gases when it comes into contact with water and therefore no longer has to be transported as dangerous goods of subclass 4.3 and provided with the appropriate transport documents.
  • the cathode scrap material according to the invention can be stored and transported without difficulty, which makes its disposal as fuel, preferably in power plants and in the production of mineral wool, cement and steel, cheaper and therefore economically more attractive than landfilling. From an ecological point of view, using it as a fuel is preferable to dumping it in a heap.
  • a further advantage of the solution according to the invention is that the presence of the hydrophobic binder, selected from wax, a waxy compound or mixtures thereof, in the cathode excavation material according to the invention further increases the calorific value of the cathode excavation according to the added proportion of hydrophobic binder, so that calorific value fluctuations between different batches of cathodic eruption are of no consequence when used as fuel.
  • the cathode waste material according to the invention it is possible to set the combustion behavior within a large degree of freedom and therefore to optimize it when used as fuel for the respective recycling process, so that it can be precisely adapted to the requirements of the corresponding further processing method.
  • An additional advantage of the invention is that the small, semolina-like fractions and dusts of the cathode eruption, which are highly reactive with water and/or atmospheric oxygen due to their high surface area, also agglomerate with the hydrophobic binder selected from wax, a waxy compound or mixtures thereof and become largely inert so that these components of the cathode eruption, which previously could only be disposed of in a complex and expensive manner due to their reactivity and size, can also be used inexpensively and safely as fuel.
  • the size of the cathode breakout that can be used for the production of mineral wool is usually limited to fractions larger than 50 mm in order to ensure a certain gas permeability of the furnace charge.
  • the method according to the invention it is also possible to agglomerate the small fractions of less than 50 mm of the cathode debris using the hydrophobic binder, selected from wax, a waxy compound or mixtures thereof, to a cathode debris material adapted in size to the specifications of the respective further processing method.
  • the hydrophobic binder selected from wax, a waxy compound or mixtures thereof
  • cathodic debris within the meaning of the invention means that the cathode debris is present with the hydrophobic binder in agglomerated form. Agglomerated means that the individual particles of the cathode eruption are bound together to form larger assemblies by means of the hydrophobic binder.
  • the cathodic spatter material of the present invention includes cathodic spall, particularly from aluminum electrolytic cells.
  • cathode spoilage is understood according to the invention as the raw material that is obtained during the mechanical breaking up and removal of the cathode lining, in particular the cathode lining of an aluminum electrolytic cell.
  • Cathode eruption within the meaning of the invention is also referred to as spent pot lining (SPL).
  • SPL spent pot lining
  • the cathode breakout is free of a hydrophobic binder.
  • first cut In practice, a distinction is made between the first cut and the second cut of a cathode breakout of aluminum electrolytic cells. While the first cut consists only of the material of the cathode lining of the electrolytic cell and thus essentially of graphite, the second cut also contains parts of the refractory lining of the electrolytic cell.
  • the cathodic breakout in the cathodic breakout material of the present invention may consist of the first cut or the second cut or a mixture of the first and second cuts. It is thus possible to adjust the cathode material that has been broken out to the specifications of the respective further processing method. For example, when using cathodic breakout as fuel in the manufacture of cement, the first and second cuts are typically used, while in the manufacture of mineral wool only the first cut is typically used.
  • the first cut of the cathode breakout typically comprises 40 to 75 wt% carbon, 10 to 20 wt% fluoride, 8 to 17 wt% sodium, up to 10 wt% alumina, up to 5 wt% aluminum (metal), 0.01-0.5 wt% cyanide, up to 6 wt% silica, 1 to 6 wt% calcium oxide, 0.1 to 0.3 wt% sulfur, and up to to 300 ppm polycyclic aromatic hydrocarbons.
  • the second cut of the cathode breakout typically comprises 0 to 20 wt% carbon, 4 to 10 wt% fluoride, 6 to 14 wt% sodium, 10 to 50 wt% alumina, 10 to 50 wt% silicon dioxide, 1 to 8% by weight calcium and 0.1 to 0.3% by weight sulfur.
  • composition of the first cut of the cathode breakout varies depending on the service life of the cathode lining before it breaks off.
  • the composition of the second cut consisting of the refractory lining and a small proportion of the cathode lining, is less dependent on the service life of the cathode lining.
  • their composition can also vary due to different ratios of the proportions of refractory lining and cathode lining when the same is broken off.
  • a mixture of the first and second cuts of the cathode breakout typically comprises 25 to 35 wt% carbon, 12 to 18 wt% fluoride, 12 to 18 wt% sodium, 12 to 18 wt% aluminum, bis up to 0.28% by weight cyanide, up to 3.5% by weight silicon dioxide, up to 3.5% by weight calcium oxide, 0.1 to 0.3% by weight sulfur and up to 165 ppm polycyclic aromatics hydrocarbons.
  • a mixture of the first and second cuts of the cathode breakout comprises 50 to 60% by weight of the first cut and 40 to 50% by weight of the second cut.
  • the cathode rupture contained in the invention cathodic material can in principle for agglomeration with a hydrophobic binder suitable shape and size.
  • the pellets, castings, briquettes or extrudates produced with it are more stable and there can be a uniform quality in terms of properties, such as the calorific value, from one individual pellet, casting, briquette or extrudate to the next individual pellet, casting , briquette or extrudate can be ensured.
  • the cathode eruption therefore preferably has a grain size of less than 50 mm, in particular less than 30 mm, particularly preferably less than 0.2 mm.
  • the cathode spall can be ground to the target fineness using a suitable grinder.
  • the individual fines can be separated into suitable fractions by classification using a sieving process.
  • different particle sizes can be advantageous. For example, grain sizes that are as small and homogeneous as possible are advantageous for the production of pellets and extrudates, while coarser grain sizes and less homogeneous grain size distributions can also be used for the production of castings and briquettes.
  • the cathodic breakout material of the present invention contains at least one hydrophobic binder selected from wax, a waxy compound, or mixtures thereof.
  • hydrophobic binder within the meaning of the invention is understood as meaning a binder which is immiscible with water. While hydrophobic binders are almost insoluble in water, they are soluble in organic, non-polar media.
  • Substances or mixtures of substances which can be kneaded at 20° C., are solid to brittle-hard and have a coarse to fine-crystalline structure are usually referred to as waxes have, are translucent to opaque in color, but not transparent, and melt above 40°C without decomposition and are already fluid a little above the melting point or have a low viscosity, have a strongly temperature-dependent consistency and solubility and can be polished under slight pressure.
  • a waxy compound is understood to mean a compound that has physical behavior similar to that of a wax.
  • Examples of natural waxes are wool wax, China wax, beeswax, preen gland fat, tallow, sugarcane wax, carnauba wax, candelilla wax, cork wax, guruma wax, ouicuri wax, cuba palm wax, espartowa wax, cotton wax, rice bran wax, flax wax, peat wax, rose wax, jasmine wax, peetha wax, myrtle wax , wax fig wax, petroleum wax, earth wax, stuff wax, vein wax, montan wax, petroleum wax and paraffin wax.
  • partially synthetic waxes are ester waxes of long-chain wax acids with monohydric fatty or wax alcohols, amides of fatty and wax acids, amide waxes based on fatty acids, such as distearylethylenediamide, ethylene disteamide, stearic acid amide, behenic acid amide, erucic acid amide, oleic acid amide, soy wax, castor wax, rapeseed wax, phthalamide waxes and acylated amides of fatty and wax acids.
  • amides of fatty and wax acids such as distearylethylenediamide, ethylene disteamide, stearic acid amide, behenic acid amide, erucic acid amide, oleic acid amide, soy wax, castor wax, rapeseed wax, phthalamide waxes and acylated amides of fatty and wax acids.
  • synthetic waxes are hydrocarbon waxes, polyolefin waxes such as polyethylene wax, EVA wax and polypropylene wax, polyester wax and Fischer-Tropsch wax.
  • the wax is preferably selected from polyolefin waxes, in particular polyethylene waxes, or paraffin waxes.
  • the waxy compound is selected from esters of glycerol with fatty acids, preferably linear carbon chains having 4 to 26, typically 12 to 22, carbon atoms, fatty acids, especially linear aliphatic monocarboxylic acids having 13 to 21 carbon atoms, and mixtures thereof, preferably stearin.
  • At least one hydrophobic binder selected from wax, a waxy compound or mixtures thereof, which has a dropping point according to DIN ISO 2176 between 35° C. and 75° C. has proven to be particularly practical.
  • Hydrophobic binders with a dropping point in this range strike a good balance between adequate strength at ambient temperature and the most energy efficient method of making the cathode breakout material. Due to the comparatively low dropping point, the amount of energy that has to be supplied to liquefy the hydrophobic binder during the production of the cathode breakout material is lower than for hydrophobic binders with a dropping point according to DIN ISO 2176 of over 75° C. and more.
  • the dropping point of the hydrophobic binder may advantageously be selected depending on the time of year and/or the climate zone in which the cathodic spoil is to be stored and transported to ensure that the hydrophobic binder is sufficiently solid at ambient temperature.
  • a hydrophobic binder with a drop point according to DIN ISO 2176 in the range between 35°C and 45°C is sufficient in a colder season and/or moderate climate zone, while in the warmer season and/or subtropical and tropical climate zones a hydrophobic binder with one Dropping point according to DIN ISO 2176 in the range between 45°C and 75°C can be advantageous.
  • the hydrophobic binder contains the smallest possible proportion of functional groups, preferably is free of functional groups.
  • functional groups are understood to mean chemical groups which differ from pure carbon-carbon or carbon-hydrogen single bonds.
  • Such a hydrophobic binder brings about a further significantly reduced reactivity of the cathode breakout material according to the invention with water and/or atmospheric oxygen, so that its storage and transport stability is further improved.
  • the higher proportion of carbon in the hydrophobic binder also increases the calorific value of the cathode debris when it is used as a fuel.
  • the cathode debris has a calorific value of between 10,500 and 31,000 kJ/kg, determined according to the RAL-GZ 724 method of the Federal Quality Association for Secondary Fuels.
  • the addition of the hydrophobic binder significantly increases the calorific value of the cathode eruption, which is usually in the range from 7500 to at most 10000 kJ/kg.
  • the cathode spoilage material according to the invention can be adapted to the requirements of the respective further processing method.
  • the cathode scrap material can advantageously be in the form of pellets, cocoons, castings, briquettes or extrudates.
  • the cathode breakout material is in the form of pellets or extrudates and contains 75 to 90% by weight cathode breakout and 10 to 25% by weight hydrophobic binder based on the total weight of the cathode breakout material.
  • Cathode spoilage in the form of pellets or extrudates that can be easily dosed is advantageous for using the cathode spoilage material as a fuel in combustions controlled by calorific value, for example in the production of cement in a rotary kiln or in the operation of a power plant.
  • the target temperature can be reliably predicted by charging with a homogeneous fuel with a known calorific value. The smaller the dosage form of the fuel, the more precisely the temperature that is reached can be regulated. Reaching a target temperature within certain limits can be important for maintaining the quality of the manufactured product.
  • the cathode spoil is in the form of briquettes and contains 60 to 80% by weight cathode spoil and 20 to 40% by weight hydrophobic binder based on the total weight of the cathode spoil.
  • Cathode spoilage material in the form of briquettes is advantageous for using the cathode spoilage material as a fuel in roughly calorific value-controlled combustion, for example in cupola furnaces used in the manufacture of mineral wool, and in batch furnaces, for example in electric arc furnaces used in steelmaking .
  • the necessary gas permeability of the feed can be achieved more easily due to the coarser form of administration compared to pellets.
  • the target temperature can be reliably set by charging with homogeneous fuel with a known calorific value.
  • the cathode breakout material is in the form of castings and contains 30 to 80% by weight cathode breakout and 20 to 70% by weight hydrophobic binder, based on the total weight of the cathode breakout material.
  • Cathode spoilage in the form of castings is advantageous for using the cathode spoilage as fuel in roughly calorific value-controlled combustions, for example in cupola furnaces used in the production of mineral wool and in batch furnaces, eg electric arc furnaces.
  • the casting molds make it possible to introduce a large amount of fuel into the process in a gas-permeable manner and at the same time enable a reliable temperature setting due to the homogeneous fuel with a known calorific value.
  • the method according to the invention is characterized in that it ensures a simple, cost-effective and energy-efficient production of the cathode excavation material.
  • the cathode spoilage material according to the invention in relation to individual technical features applies correspondingly to the corresponding technical features of the method according to the invention.
  • Step (a) of the method according to the invention provides for the provision of cathodic breakout, in particular aluminum electrolytic cells.
  • the provision of the cathode breakout in step (a) can take place in any shape and size of the cathode breakout and is only limited by the technical possibilities of transporting the cathode breakout.
  • both coarse pieces and plates of cathode debris more than 1 m in length and very fine dusts of cathode debris and mixtures with a wide variety of grain sizes and plate sizes, such as are usually obtained when a cathode lining is mechanically demolished can be used in step (a).
  • step (b) of the method the broken cathode is comminuted in at least one comminution device.
  • a comminution device known to those skilled in the art can be used as at least one comminution device.
  • the at least one comminution device in step (b) is preferably a mill or a crusher.
  • the at least one comminution device causes a reduction in the plate and/or particle size of the cathodic breakout.
  • the cathode eruption is fractionated by a separating device.
  • separating devices can be used which ensure a homogeneous particle size of the cathode debris.
  • the separating device in step (c) is a screen.
  • other separating devices are also conceivable with which a fine fraction of a specific grain size of the cathode sliver can be separated from the cathode sliver comminuted in step (b).
  • the fractionation in step (c) can preferably take place at the same time as the comminution in step (b). However, it is also conceivable that the fractionation takes place only after the comminution in step (b).
  • the method according to the invention provides that in step d) the cathode debris is mixed with at least one hydrophobic binder selected from wax, a waxy compound or mixtures thereof in a mixing device.
  • the at least one hydrophobic binder is preferably metered into the mixing device in step (d) in liquid form or liquefied by heating in the mixing device.
  • the dosing in liquid form can be achieved, for example, by supplying the hydrophobic binder to the mixing device from a separate heated reservoir.
  • the mixing device itself can be heated or that the wax is liquefied by the energy input of the mixing unit in the mixing device.
  • Steps (b) to (d) of the process according to the invention are carried out under an inert gas atmosphere.
  • an inert gas atmosphere This is necessary because the cathode eruption, in particular the fine fractions thereof produced in step (b), are highly reactive with water and/or atmospheric oxygen, which, as already explained at the beginning, can lead to heat development, toxic gas development and ignition.
  • Such a reaction must therefore be avoided at all costs from a safety perspective.
  • noble gases such as helium, neon, argon, krypton and xenon, as well as nitrogen, can be used as the inert gas.
  • nitrogen is preferred according to the invention.
  • step (e) of the process according to the invention the mixture obtained in step (d) is portioned.
  • the portioning in step (e) is preferably selected from casting, briquetting, extruding or pelletizing.
  • the hydrophobic binder cocoon can be a geometric hollow shape, in particular a hollow sphere or a hollow cylinder, with a hollow sphere being preferred.
  • step (e) The portioning in step (e) would take place for the hollow sphere-cocoon embodiment in such a way that the mixture obtained in step (d) is filled into a solid hollow hemisphere made of the hydrophobic binder and the other solid hollow hemisphere after heating and thus softening the surrounding The edge of the hollow hemisphere is then placed like a lid on the hollow hemisphere filled with the cathode rupture, so that the cathode rupture is completely enclosed by the solid cocoon of hydrophobic binder.
  • step (e) of the process according to the invention different proportions of cathode debris and binder are preferably mixed in step (d).
  • the portioning is pelletizing or extruding and in step (d) 75 to 90% by weight cathode slag and 10 to 25% by weight hydrophobic binder based on the total weight of the mixture of cathode slag and hydrophobic binder , mixed.
  • the portioning is briquetting and in step (d) 60 to 80% by weight of cathode slag and 20 to 40% by weight of hydrophobic binder, based on the total weight of the mixture of cathode slag and hydrophobic binder, mixed.
  • the portioning is in-mold casting and in step (d) 30 to 80% by weight of cathode eruption and 20 to 70% by weight of hydrophobic binder, based on the Total weight of mixture of cathode spall and hydrophobic binder, mixed.
  • the method according to the invention provides that the cathode debris is removed in step (f).
  • the cathode debris removed in step (f) is preferably present in the administration forms mentioned above.
  • the broken-out cathode material Before removal in step (f), the broken-out cathode material can be treated with a separating agent in order to prevent the broken-out cathode material from sticking together during storage and transport.
  • a separating agent in order to prevent the broken-out cathode material from sticking together during storage and transport.
  • Powdered substances are conceivable as release agents.
  • Exemplary release agents are calcium carbonate, talc or silicates.
  • the process according to the invention can be carried out semi-continuously or continuously.
  • the invention relates to the use of the cathode spoilage material according to the invention as a fuel, preferably in power stations and in the production of mineral wool, cement and steel.
  • the combustion behavior of the cathode scrap material must be adapted to the different requirements of the respective recycling process.
  • FIG 1 1 is a schematic representation of an embodiment of the method of the present invention for producing cathode spoil.
  • a nitrogen-inerted mill with the prepared cathode burst 2 with a particle size of less than 50 mm is charged via a vibrating hopper 3 . If fragments are too coarse or the range in size distribution is too large to be fed to a mill, a nitrogen-inerted crusher can also be installed upstream.
  • the served cathode breakout 2 acts at the same time as a dust separator.
  • Using a sieve 4 close to the ground the final grain size with which the fine fraction of the cathode debris is discharged from the mill into the heated mixer 5 is determined.
  • liquefied wax is added via a dosing unit 6 to a concentration of 20 to 40% by weight of wax based on the total weight of the cathode spoilage material.
  • the wax was liquefied beforehand in a heated wax storage tank 7 .
  • the mill 1, the crusher that may be connected upstream and the addition of wax via the dosing unit 6 are stopped.
  • the direction of mixing rotation in the mixer 5 is changed and the cathode spoilage material/wax mixture is poured into slightly conical molds 8 . After cooling to room temperature the finished cathode spoilage material can be removed from the molds 8 and is therefore available as a casting.
  • the grinding process took place under a nitrogen atmosphere and was carried out with a target fineness of 10% > 90 ⁇ m. This means that after grinding was complete, 90% of the cathode breakout was smaller than 90 ⁇ m, the remaining 10% was between approx. 150 and 200 ⁇ m.
  • the pelleting was carried out in a semi-continuous process, in that the ground cathode debris was tracked in such a way that the pellet removal (falling over the edge) turned out to be proportional to the mass.
  • the preheated, liquid wax was dosed (or sprayed on) in the appropriate ratio.
  • the angle of attack of the pelletizing disk during the production of the pellets was 30° to the perpendicular and the number of revolutions was 30 rpm.
  • the "original substance” given in Table 1 means the pellets as they were removed from the pelletizing machine.
  • “Dry matter” refers to the pellets that have been subjected to drying in accordance with DIN EN 14346 after removal from the pelletizing machine.
  • castings were made.
  • a sieve fraction ⁇ 3 mm was separated from the fine fraction of the cathode debris and used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)
EP21210576.1A 2021-11-25 2021-11-25 Matière à base de brasque usée stable au stockage, son procédé de fabrication, ainsi que son utilisation en tant que combustible Pending EP4186963A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP21210576.1A EP4186963A1 (fr) 2021-11-25 2021-11-25 Matière à base de brasque usée stable au stockage, son procédé de fabrication, ainsi que son utilisation en tant que combustible
PCT/EP2022/083258 WO2023094584A1 (fr) 2021-11-25 2022-11-25 Matériau à base de brasque usée stable au stockage, procédé de production correspondant et son utilisation comme combustible
CN202280077929.7A CN118302506A (zh) 2021-11-25 2022-11-25 存储稳定的阴极废料、其制造方法及其作为燃料的应用
AU2022397819A AU2022397819A1 (en) 2021-11-25 2022-11-25 Storage-stable spent potlining material, method for the production thereof, and use of the same as fuel
CA3239118A CA3239118A1 (fr) 2021-11-25 2022-11-25 Materiau pour revetement de cuves epuise stable au stockage, son procede de fabrication et son utilisation comme combustible
US18/667,403 US20240301313A1 (en) 2021-11-25 2024-05-17 Storage-Stable Spent Potlining Material, Method for the Production Thereof, and Use of the Same as Fuel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP21210576.1A EP4186963A1 (fr) 2021-11-25 2021-11-25 Matière à base de brasque usée stable au stockage, son procédé de fabrication, ainsi que son utilisation en tant que combustible

Publications (1)

Publication Number Publication Date
EP4186963A1 true EP4186963A1 (fr) 2023-05-31

Family

ID=78789904

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21210576.1A Pending EP4186963A1 (fr) 2021-11-25 2021-11-25 Matière à base de brasque usée stable au stockage, son procédé de fabrication, ainsi que son utilisation en tant que combustible

Country Status (6)

Country Link
US (1) US20240301313A1 (fr)
EP (1) EP4186963A1 (fr)
CN (1) CN118302506A (fr)
AU (1) AU2022397819A1 (fr)
CA (1) CA3239118A1 (fr)
WO (1) WO2023094584A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988006572A1 (fr) 1987-02-27 1988-09-07 Gee Kenneth H Nouvelle methode d'exploitation de cubilots de laine minerale et d'utilisation d'un garnissage de creuset d'aluminium electrolytique use
US4927459A (en) * 1989-03-17 1990-05-22 Imco Recycling Inc. Treatment of aluminum reduction cell linings combined with use in aluminum scrap reclamation
DE10146614A1 (de) * 2001-02-21 2003-01-23 Rockwool Mineralwolle Verfahren zur Herstellung von Dämmstoffen aus Mineralfasern
US20050053410A1 (en) * 2003-09-10 2005-03-10 Council Of Scientific And Industrial Research Simple and efficient process for the preparation of pencil lead from spent pot-liners
US20110081284A1 (en) * 2009-10-02 2011-04-07 Mark Weaver Treatment of bauxite residue and spent pot lining
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

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4763585A (en) * 1987-09-08 1988-08-16 Ogden Environmental Services Method for the combustion of spent potlinings from the manufacture of aluminum
AT510686B1 (de) * 2011-02-23 2012-06-15 Sgl Carbon Se Verfahren zum aufarbeiten von verbrauchtem kohlenstoffhaltigen kathodenmaterial
CA2907458C (fr) * 2013-03-26 2020-07-14 Standard Brands (Uk) Limited Buche et procede de fabrication d'une buche
CN105908217A (zh) * 2016-06-24 2016-08-31 登封电厂集团铝合金有限公司 铝电解槽旧阴极炭块制作侧部炭块的方法
TWI633181B (zh) * 2017-06-12 2018-08-21 于駿傑 固態金屬燃料之製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988006572A1 (fr) 1987-02-27 1988-09-07 Gee Kenneth H Nouvelle methode d'exploitation de cubilots de laine minerale et d'utilisation d'un garnissage de creuset d'aluminium electrolytique use
US4927459A (en) * 1989-03-17 1990-05-22 Imco Recycling Inc. Treatment of aluminum reduction cell linings combined with use in aluminum scrap reclamation
DE10146614A1 (de) * 2001-02-21 2003-01-23 Rockwool Mineralwolle Verfahren zur Herstellung von Dämmstoffen aus Mineralfasern
US20050053410A1 (en) * 2003-09-10 2005-03-10 Council Of Scientific And Industrial Research Simple and efficient process for the preparation of pencil lead from spent pot-liners
US20110081284A1 (en) * 2009-10-02 2011-04-07 Mark Weaver Treatment of bauxite residue and spent pot lining
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

Also Published As

Publication number Publication date
AU2022397819A1 (en) 2024-06-13
CA3239118A1 (fr) 2023-06-01
US20240301313A1 (en) 2024-09-12
WO2023094584A1 (fr) 2023-06-01
CN118302506A (zh) 2024-07-05

Similar Documents

Publication Publication Date Title
AT516369B1 (de) Flussmittel, Verfahren zu seiner Herstellung, Agglomerationsgemisch und Verwendung von Schlacke aus der Sekundärmetallurgie
CH649233A5 (de) Verfahren zur ab- und endlagerung von abfallstoffen.
WO1993011269A1 (fr) Procede et composition s'utilisant dans le recyclage de poussiere de hauts fourneaux contenant des metaux
DE69507501T2 (de) Aufbereitung von abfallstoffen
WO2012010254A1 (fr) Procédé de briquetage de battitures de laminoir
EP3431617B1 (fr) Granulés en tant qu'agrégat pour processus métallurgiques et leur procédé de fabrication et d'utilisation
WO2009077425A1 (fr) Procédé de fabrication de matériaux de construction à partir de scories d'aciérie
EP0131848B1 (fr) Procédé pour l'élimination de corps étrangers de la circulation de matériaux dans la préparation électrothermique du phosphore jaune
EP3577070B1 (fr) Procédé pour fabriquer une briquette et briquette fabriquée selon ledit procédé
EP0526697B1 (fr) Procédé et appareil pour le traitement de déchets de laine minérale
EP4186963A1 (fr) Matière à base de brasque usée stable au stockage, son procédé de fabrication, ainsi que son utilisation en tant que combustible
EP2210963B1 (fr) Briquetage de battitures en utilisant une pulpe à papier
DE3347685C1 (de) Verfahren zur Herstellung von Ferromangan
EP0786532A2 (fr) Briquette contenant des résidus silicieux, utilisable comme additif dans la métallurgie et procédé pour sa fabrication
DE69213541T2 (de) Entschwefelungsmittel für Roheisen, aus Calciumkarbid und organisches Bindemittel
DE102005023525A1 (de) Verfahren zur Zerkleinerung von Metallspänegemischen und zur legierungsspezifischen Rückgewinnung der Metallspäne
DE69620450T2 (de) Verfahren zur verwendung kohlenstoffhaltiger materialien bei der elektrolytischen produktion von aluminium
DE69404034T2 (de) Agglomerieren durch Extrudieren
JP6069976B2 (ja) 水砕スラグ及びその製造方法
EP2768988A2 (fr) Agent de désulfuration contenant du bitume, procede de fabrication et son utilisation
EP3947278B1 (fr) Procédé de préparation d'agglomerats contenant du silicium métallique
JP6315043B2 (ja) 水砕スラグの製造方法
DE102020101700A1 (de) Verfahren zur Optimierung der Förder-, Transport- und Lagereigenschaften eines Industriebrennstoffs
JP4857541B2 (ja) 固形バインダーおよび固形バインダーを用いた成型炭とコークスの製造方法
US20120180598A1 (en) Process using fly ash to create chunks of raw material for iron or steel mill activities.

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20231129

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR